Degradation of Mechanical Properties of

Cr-Mo-V and 2.25Cr-1Mo Steel Components After

Long-Term Service at Elevated Temperatures
N.S. C H E R U V U

The influence of operating temperature on in-service degradation of mechanical properties of

high temperature stream turbine components has been investigated. Material samples for this
study were taken from a Cr-Mo-V rotor and several 2 . 2 5 C r - l M o cast steel components which
had operated over 200,000 hours. The test results revealed that the degree of in-service deg-
radation of strength, toughness, and the fracture appearance transition temperature of both steels
were very sensitive to the service temperature. Both steels softened only when they were ex-
posed at a temperature greater than 454 ~ (850 ~ and the degree of softening increased with
further increase in service temperature. In Cr-Mo-V steel, the loss in strength was accompanied
by an improvement in ductility and toughness. Despite softening of 2.25Cr-1Mo steel in service,
elevated temperature exposure resulted in a marked decrease in ductility and toughness. The
loss of toughness in this steel was in part irreversible. In contrast, a severe increase in fracture
appearance transition temperature, due to reversible temper embrittlement, occurred in both
steels at a service temperature of around 427 ~ (800 ~ but not at the highest service tem-
perature. In fact, the Cr-Mo-V steel did not temper embrittle as a result of service exposure at
the highest operating temperature investigated. These results are rationalized in terms of changes
in microstructure and grain boundary chemistry that occur in service as a function of operating
temperature.

I. I N T R O D U C T I O N of impurities such as P, Sn, As, and Sb to the grain

Low alloy ferritic steels of the Cr-Mo-V and C r - M o
type are extensively used for high temperature applica-
tions in the power, chemical, and oil industries, for their
excellent elevated temperature strength and good resis-
tance to oxidation and hydrogen embrittlement. These
steels are used in the power industry for components such
as high pressure (HP) and intermediate pressure (IP) fos-
sil steam turbine rotors, cylinders, blade rings, nozzle
chambers, steam chests, steam pipes, boilers, and head-
ers. The inlet and exhaust temperatures of a typical fossil
HP or IP turbine element are 538 ~ (1000 ~ and 288 ~
(550 ~ respectively. Thus, the steam turbine compo-
nents operate in the temperature range where creep and
temper embrittlement is a concern. Though Cr-Mo-V and
Cr-Mo steels were believed to be immune to temper em-
brittlement, the results generated over the last decade in-
dicate that they are highly susceptible to temper
embrittlement, tl,2,31 Thus, prolonged service exposure of
these turbine components leads to degradation of their
mechanical properties. Hence, the remaining service life
of these components is limited by the extent of in-service
material degradation that has occurred. Evaluation of in-
service material degradation after long-term service is
therefore necessary for meaningful remaining service life
assessment.
When low alloy steel components are exposed to el-
evated temperature during service, their properties de-
teriorate due to changes in microstructure and diffusion
N.S. CHERUVU is Senior Engineer, Power Systems Division,
Westinghouse Electric Corporation, The Quadrangle, University Blvd.,
Orlando, FL 32826.
Manuscript submitted April 22, 1988.
boundaries. It is now well established that segregation
of impurities at the grain boundaries temper embrittles
these steels. The segregation-induced temper embrittle-
ment is manifested as an increase in the transition
temperature and is reversible. The changes in micro-
structure, such as carbide coarsening and precipitation
of more stable carbides during service, can cause soft-
ening and irreversible embrittlement. The carbide-
induced embrittlement is manifested as a decrease in the
impact toughness without affecting the ductile-to-brittle
transition temperature t4'5'6] and is irreversible, unlike
segregation-induced embrittlement.
Recent investigations by several investigators reveal-
ed that Cr-Mo, tS~ 2 . 2 5 C r - l M o , t7'81 and Cr-Mo-V rotor
steels t9'~1~ had softened significantly as a result of ele-
vated temperature exposure. Zhe e t a l . t1~ studied the in-
fluence of operating temperature on the hardness of a
rotor, which was referred to as Buck rotor, after sev-
enteen years of service and reported that the steel had
softened when the service temperature was greater than
308 ~ (586 ~ However, this temperature is too low
to cause any significant changes in microstructure during
service since the rotor forgings are normally tempered,
prior to placing them in service, at a considerably higher
temperature than the temperature at which onset of soft-
ening was reported. The observed m a x i m u m difference
in hardness between the hot and cold locations of the
Buck rotor was only 5 Rc points. Generally, a variation
of 70 MPa (10 ksi) in tensile strength, or 5 Rc points in
hardness, from the one end to the other is not atypical
in 1950 vintage rotor forgings, t~2] Hence, it was not clear
whether the observed variation in hardness between the
cold and hot locations was due to softening or due to
variation in the original properties of the Buck rotor.

METALLURGICAL TRANSACTIONS A VOLUME 20A, JANUARY 1989--87

 Furthermore, the results of Nishizaka et al.~SJ and Qu
and Kuo [6] on service-exposed Cr-Mo and 2.25Cr-lMo-
0.25V steels have shown that these steels embrittle due
to precipitation or change in morphology of carbides
during service. It was not known from the studies of Zhe
et al. ~1~ and Cheruvu et al. Bq whether or not softening
of a 1Cr-lMo-0.25V rotor steel during service was as-
sociated with precipitation-induced embrittlement.
The results t9-1~'~3~ of service-exposed Cr-Mo-V rotors
further revealed that these steels displayed the greatest
susceptibility to reversible temper embrittlement in re-
gions where the service temperature was around 427 ~
(800 ~ Though Cr-Mo steel turbine cylinders operate
over a range of temperatures, the influence of service
temperature on temper embrittlement behavior of these
steels is not known. Therefore, the present study was
undertaken to evaluate systematically the influence of
service temperature on the softening and embrittlement
behavior of Cr-Mo-V and 2 . 2 5 C r - l M o steels: The pri-
mary objectives of this study were:
(I) To determine the m a x i m u m service temperature up
to which no softening occurs during service for both steels.
(II) To establish susceptibility of these steels to precip-
itation or carbide-induced embrittlement.
( l i d To identify the service temperature at which severe
temper embrittlement occurs in 2 . 2 5 C r - l M o steel.
To identify reversible and irreversible embrittlements,
impact tests in the as-service-exposed and de-embrittled
conditions, fractographic characterization of Charpy
specimen fracture surfaces and Auger analysis of frac-
ture surfaces for grain boundary chemistry were carried
out in this study.
II. EXPERIMENTAL PROCEDURE
A . Material and Microstructure
Material for this study was taken from a combined HP
and IP Cr-Mo-V rotor, and 2.25Cr-lMo steel flow guide,
blade ring, and nozzle chamber castings, which had op-
erated over 200,000 hours. From the rotor, the IP blade
groove walls 1 through 6 were machined as rings and
were identified as rings 1 through 6. Rings 1, 2, 3, and
6 were used for this study. In addition to matching the
rings, trepan samples were also drilled from the HP
d u m m y (hot) and cold locations of the rotor. The test
material locations are shown in Figure 1, and service
temperature at these locations is given in Table I. The
flow guide, blade ring, and nozzle chamber castings were
co~~! v~o~
Fig. 1 - - T e s t sample locations in the HP-IP rotor.
88--VOLUME 20A, JANUARY 1989
Table I. Operating Metal Temperatures of Test
Material Locations of the HP-IP Rotor
Service
Temperature
Location ~ ~
HP dummy (hot) 985 529
Ring 1 850 454
Ring 2 975 524
Ring 3 950 510
Ring 6 870 466
Cold 550 288
operated at temperatures of 454 ~ (850 ~ 427 ~
(800 ~ and 538 ~ (1000 ~ respectively.
The rotor steel was austenitized at 1010 ~ (1850 ~
air cooled, tempered at 666 ~ (1230 ~ and then fur-
nace cooled from the tempering temperature. A review
of original test results revealed that the rotor had uniform
tensile properties from the one end to the other (Table
II). The original heat treatment details of 2.25Cr-lMo
castings are not available. However, all three castings
were made to the same specification in 1953. The spec-
ification applicable at that time indicated that these cast-
ings were normalized and tempered at a temperature
greater than 665 ~ to produce minimum tensile and yield
strengths of 552 and 276 MPa (80 and 40 ksi), respec-
tively. The chemical composition of the test materials is
shown in Tables III and IV. The chemistry of the casting
used to generate the A S T M data base t141 is also given in
Table IV for comparison since original data for the sub-
ject 2 . 2 5 C r - l M o components are not available and this
casting is referred to as the ASTM casting. The chem-
istry and tensile properties of the A S T M casting com-
plied with the specification requirements. The chemistry
of all components reasonably agrees with that for the
A S T M casting.
The microstructure of the rotor steel was essentially
upper bainite with an average prior austenite grain size
of A S T M # 3 . The microstructure of the three castings
exhibited a duplex structure containing ferrite and bain-
ite, which was a typical structure for normalized and
tempered 2.25Cr- 1Mo steel. Typical microstructures for
Cr-Mo-V and 2.25Cr-1Mo steels after service are shown
in Figure 2.
B. Test Conditions
Tensile specimens with a gage length of 35.6 m m
(1.4 in.), a diameter of 9.1 m m (0.36 in.), and standard
size V-notch Charpy specimens were machined from each
test location of the rotor, flow guide, blade ring, and
nozzle chamber. A portion of the Charpy samples ma-
chined from Rings 2, 3, and 6, the flow guide, and the
nozzle chamber were given a de-embrittling treatment of
638 ~ (1180 ~ for 1 hour and then cooled. Combi-
nation smooth bar-notch bar type creep rupture speci-
mens, with a theoretical stress concentration factor of
approximately 4 at the notch, were machined from the
hot and cold locations of the rotor and the three cast-
ings. The dimensions of a combination creep rupture
specimen were given elsewhere. 1151 These specimens
were utilized for creep rupture tests to evaluate potential
METALLURGICAL TRANSACTIONS A
 Table II. The Original Tensile Properties at Various Locations of the HP-IP Rotor
Tensile Strength Yield Strength
Location MPa Ksi MPa Ksi Pet Elong. Pet R A
HP d u m m y (hot) 938 136 786 114 12 25
Near IP blade groove walls 931 135 779 113 12 26
Cold location 945 137 800 116 13 25

Table III. Chemistry of the HP-IP Rotor (Wt Pet)

C Mn Si Ni Cr Mo V S P Sn As Sb
After service 0.33 0.73 0.22 0.11 1.05 1.15 0.25 0.026 0.031 0.011 0.007 0.001
Original test report 0.31 0.70 0.19 0.18 1.07 1.35 0.24 0.026 0.030 -- -- --
Rotor forging heat treatment for properties: austenitized at 1010 ~ (1850 ~ cooled; tempered at 666 ~ (1230 ~ cooled.

Table IV. Chemistry of the Stationary Components ( W t Pet)

Component C Mn Si Ni Cr Mo S P Sn As
F l o w guide 0.16 0.57 0.40 0.07 2.60 0.74 0.015 0.015 0.014 0.017
Blade ring 0.16 0.60 0.44 0.07 2.63 0.76 0.020 0.016 0.013 0.016
Nozzle chamber 0.11 0.58 0.48 0.07 2.22 0.68 0.035 0.021 0.021 0.015
A S T M castings tl41 0.17 0.56 0.40 -- 2.32 0.93 0.036 0.030 -- --
Heat treatment: All castings were normalized and tempered.

Fig. 2--Microstmctures of (a) cold location of Cr-Mo-V rotor-exposed at 288 ~ (b) 2.25Cr-lMo flow guide-exposed at 454 ~ (c) 2.25Cr-
1Mo blade ring-exposed at 427 ~ (d) 2.25Cr-lMo nozzle chamber-exposed at 538 ~

METALLURGICAL TRANSACTIONS A VOLUME 20A, JANUARY 1989--89

notch-sensitive behavior of the subject steels. All tensile 250 350
~
450
--140
specimens were tested at room temperature. The Charpy
specimens were subjected to impact testing to determine
TENSILE STRENGTH
the 50 pct fracture appearance transition temperature
90C- 130
(FATT). Approximately 6 to 10 specimens were utilized
g
to generate a full Charpy curve. The creep rupture spec- v
imens were tested at different temperatures and stresses. z
~_ 825. 120 5o
A few specimens from the castings were also tested at
f=
a stress of 110 MPa (16 ksi) and different temperatures
YIELD STRENGTH 0 0 9
i
since these results were successfully used for remaining m 110 ~o ~
F- 750
service life assessment of components. [16,~7~ g
I
C. Fractography and Prior Austenite 100
~. 675
Grain Boundary Chemistry
[ ~
~ ~
REDUCTION
OAREA F
9 DII
!
The fracture surfaces of selected broken Charpy spec- 90 20
imens tested at room temperature were examined using 600
a Cambridge Scanning Electron Microscope (SEM) Model ELONGATION

5150 B to determine the fracture mode. In addition, a I

circumferentially notched cylindrical specimen was ma-
chined from each of these Charpy specimens, and frac-
tured in the ultra-high vacuum chamber of the Auger
Spectrometer at room temperature. Each fracture surface
was analyzed in the chamber for grain boundary chem-
istry at ten spots with a primary beam size of 8 /zm.
III. RESULTS
A. Tensile Properties
1. Cr-Mo-V steel
The influence o f operating temperature on tensile
properties of the rotor steel is shown in Figure 3. The
tensile and yield strengths were almost unaffected as a
result of service exposure at temperatures up to approx-
imately 454 ~ (850 ~ and then dropped with further
increasing service temperature. However, the ductility,
as measured by pet elongation and reduction of area, de-
creased slightly with increasing temperature up to about
454 ~ (850 ~ and then sharply increased with increas-
ing temperature.
A comparison of results of the specimens obtained from
the hot location before (Table II) and after service (Fig-
ure 3) revealed that the tensile and yield strengths de-
creased from 939 MPa (136 ksi) to 855 MPa (124 ksi),
and 786 MPa (114 ksi) to 686 MPa (99.5 ksi), respec-
tively, and the reduction of area increased from 24.8 pet
to 39.1 pet (by 56 pet) due to service exposure.
2. 2.25Cr-lMo steel
The results of room temperature tensile properties of
2 . 2 5 C r - l M o steel castings after service are summarized
in Table V. Since the original properties are not avail-
400 6O0 800 1000
~
OPERATING TEMPERATURE, ~
Fig. 3--Variation of tensile properties of Cr-Mo-V rotor steel with
service temperature. The solid symbols denote the original properties"
of the rotor steel at the corresponding locations.
able, the present results are compared with those re-
ported for an unexposed ASTM casting. I14] The tensile
properties of the flow guide and blade ring castings after
service were higher than those of the unexposed steel,
suggesting that the original properties of the subject cast-
ings were above the minimum specified values. These
results further suggest that 2.25Cr-lMo steel does not
soften when it is exposed at or below 454 ~ (850 ~
The yield and the tensile strengths of the nozzle chamber
steel casting were, however, significantly lower than that
of flow guide and blade ring castings, indicating that this
steel had softened due to service exposure at 538 ~
(1000 ~ In contrast to the results of Cr-Mo-V steel,
the pet elongation and reduction of area of the nozzle
chamber casting were not improved as a result of soft-
ening. Both pct elongation and reduction of area dropped
somewhat as compared to the results of the other two
service-exposed castings.
B. Creep Rupture
1. Cr-Mo-V steel
Creep rupture results of Cr-Mo-V steel are summa-
rized in Table VI. All creep rupture specimens obtained
from both cold and hot locations failed first in the notch,
indicating that the rotor steel was notch sensitive. These
results suggest that the notch sensitivity of the steel was

Table V. Comparison of Room Temperature Tensile Properties of 2.25Cr-lMo Steel Components

After Service with Unexposed ASTM Casting
Temperature
Reduction
Exposure Tensile Strength Yield Strength Elongation of Area
Component ~ ~ MPa Ksi MPa Ksi Pet Pet
Flow guide 454 850 578.8 84.0 405.1 58.8 31.2 69.4
Blade ring 427 800 579.5 84.1 397.6 57.7 30.2 68.1
Nozzle chamber 538 1000 516.8 75.0 250.1 36.3 29.5 55.6
Unexposed ASTM castings I~< -- -- 532.0 80.0 375.0 53.0 27.0 51.0

90--VOLUME 20A, JANUARY 1989 METALLURGICAL TRANSACTIONS A

 Table VI. Creep Rupture Results of Cr-Mo-V Rotor Steel
Rupture Time
Hours
Test Temperature StresS Notch Smooth
Location ~ ~ MPa Ksi Bar Bar Pct Elong. Pct RA
Cold 510 950 345 50 1197 3375 0.6 0*
524 975 324 47 817 3896 0.1 1.0
538 1000 310 45 868 3856** -- --
566 1050 234 34 1192 5294 0* 0*
Hot 510 950 345 50 1811 2532 5.9 9.0
510 950 345 5O 1384 2095 7.5 15.4
524 975 345 47 762 1767 3.8 7.8
538 1000 310 45 705 1585 4.0 6.8
566 1050 234 34 1010 2393 4.3 7.0
*No measureable change in dimensions was noted.
**Not failed.

not due to elevated temperature exposure during service,
but can be attributed to the temperature at which the ro-
tor was austenitized.t~8,19~ F o l l o w i n g the initial notch fail-
ure, all these specimens were tested for a smooth-bar
failure.
Several interesting observations can be m a d e from the
creep rupture results. First, service exposure at 530 ~
(985 ~ reduced s m o o t h - b a r rupture life by approxi-
mately a factor of two, without significantly affecting
notch bar rupture life, as c o m p a r e d to that of specimens
from the cold location. A l t h o u g h service exposure led to
softening at the hot location, the notch rupture life was
not increased as a result of softening. H o w e v e r , consis-
tent with the tensile ductility results, the creep rupture
ductility of the rotor steel also i m p r o v e d c o n s i d e r a b l y as
a result of service exposure at 529 ~ (985 ~
2. 2 . 2 5 C r - l M o steel
The creep rupture results o f 2 . 2 5 C r - l M o cast steel
c o m p o n e n t s are s u m m a r i z e d in T a b l e VII. In this case,
all specimens failed first in the gage section, suggesting
that these steels were not notch sensitive. F o l l o w i n g the
initial failure in the s m o o t h - b a r section, no tests were
conducted on the notch section. In a sharp contrast to
C r - M o - V results, these steels exhibited good creep rup-
ture ductility; reduction of area of all specimens was in

Table VII. Creep Rupture Results of 2.25Cr-lMo Steel Castings

Test Rupture
Temperature Stress Time,
Component ~ ~ MPa Ksi Hours Pct Elong. Pct RA
Flow guide 482 900 241 35 185 34.8 79.3
510 950 193 28 409 32.1 81.8
538 1000 145 21 1113 34.4 86.6
566 1050 110 16 2074 31.5 88.9
593 1100 82 12 7043 -- 82.6
593 1100 110 16 517 45.0 84.6
579 1075 110 16 1203 -- 87.2
566 1050 110 16 3144 43.2 86.1
552 1025 110 16 7019 21.5 85.2
538 1000 110 16 9000 not failed --
Blade ring 482 900 241 35 415 27.1 78.9
510 950 193 28 453 37.1 83.1
538 1000 145 21 1826 47.9 86.5
566 1050 110 16 3623 44.7 90.3
593 1100 82 12 8155 -- 87.6
Nozzle chamber 552 1025 110 16 649 49.2 84.9
566 1050 110 16 366 54.1 88.9
566 1050 110 16 320 55.6 90.3
579 1075 110 16 127 54.5 87.3
593 1100 110 16 63 43.4 88.0
538 1000 110 16 2311 53.7 83.5
579 1075 90 13 1069 47.1 89.9
566 1050 90 13 2197 44.6 88.0
593 1100 69 10 4531 50.4 92.4
621 1150 48 7 5986 35.5 89.9

METALLURGICAL TRANSACTIONS A V O L U M E 20A, J A N U A R Y 1 9 8 9 - - 9 1

the range of 79 to 92 pct. No apparent differences in
creep ductility were noted among the three castings.
Figure 4 is a plot of the logarithm of stress vs a time- FLOW GUIDE
EXPOSED AT 4540C (850~
temperature (Larson-Miller) parameter for three cast- 625
1150
ings. These results showed that the creep rupture strength NOZZLE CHAMBER
[ ] EXPOSED AT 538~ (1000~
of the flow guide and blade ring castings were almost
identical. The nozzle chamber steel casting had signifi- 600
O
o
1100
cantly lower creep rupture strength as compared to the
other two castings. This drop in rupture strength was not P-
575
accompanied by an improvement in creep rupture duc- ==
1050
tility. The lower creep rupture strength of the nozzle
chamber casting can be explained in terms of softening 550
that occurred in service.
1000
Variations of rupture time with temperature at an ap-
plied stress of 110 MPa (16 ksi) for the flow guide and 525

nozzle chamber castings are illustrated in Figure 5. At

950
all test temperatures investigated, the specimens from the
nozzle chamber exhibited an order of magnitude and I I I
100 1000 10,000
shorter rupture life than those from the flow guide. The
T I M E TO F A I L U R E , H O U R S
implication of these results is that the nozzle chamber
has a shorter remaining service life at any given tem- Fig. 5--After service rupture life of 2.25Cr-lMo cast steels as a func-
perature than the other two cast components. tion of test temperature at 16 ksi (110 MPa).

C. Impact Properties
1. Cr-Mo-V steel
Variation of FATT and upper shelf energy of the
Cr-Mo-V rotor steel as a function of service temperature
is shown in Figure 6. The F A T T increased with increas-
ing operating temperature up to approximately 427 ~
(800 ~ reached a m a x i m u m value, then sharply de-
creased with further increase in temperature. The upper
shelf energy exhibited a reverse trend of FATT; it de-
creased with increasing temperature to around 427 ~
(800 ~ and then increased with further increase in tem-
perature. The improvement in upper shelf energy above
this temperature is consistent with the plane strain frac-
T (K) (20 + log tt) x 10 .3
18 20
60 2.25 Cr - 1 M o STEEL CASTINGS
A FLOW GUIDE
9 B L A D E RING
[] NOZZLE CHAMBER
ture toughness results reported by CheruvuJ 9] Further-
more, it is interesting to note that FATT of the samples
machined from the hot location exposed at the highest
temperature was lower than that of cold location, and
this drop in F A T T was, in part, due to softening. The
improvement in upper shelf energy of the samples from
the hot location can also be attributed to the drop in ten-
sile strength.
The FATT and upper shelf energy of the samples in
the de-embrittled condition are also shown in Figure 6.
The de-embrittling treatment lowered the FATT of the
samples from Ring 6 from 249 ~ (480 ~ to 168 ~
(335 ~ suggesting that the embrittlement that occurred
in service was reversible. In addition, the FATT and up-
per shelf energies of the specimens from the hot location
22
in the service-exposed condition were comparable to those
of de-embrittled specimens.
Figure 7 shows the typical fracture mode of broken
Charpy specimens from the cold location, Ring 1, and
320
the hot location. The fracture mode of the specimens from
Ring 1, which was exposed at 454 ~ (850 ~ was

~
204 300 400 50o 590
160
500 TRANSITION UPPER SHELF
20 TEMPERATURE ENERGY
250 OSERVICE EXPOSED 9 V SERVICE EXPOSED
9 DE-EMBRI'i'FLE D 9 DE-EMBRITrLED
# _~ 45O

80
i 400 9
10 2oo

i? ~ E4

O t=
m \\ = 40 w , ~
40 -= aso 99 -Z~ "4, t ~tu
150 300 ,17 o~ u ~z

3'0 ~'~, 3'~ 3'5 ~'~ 27 t=

T (R) (20 + l o g tf) x 10 -3 25~ 600 800 1000
LARSON - M I L L E R PARAMETER OPERATING TEMPERATURE, ~

Fig. 4 - - C r e e p rupture strength of 2.25Cr-lMo cast steel after Fig. 6--Variation of FATT and upper shelf energy of Cr-Mo-V steel
service. with service temperature.

92--VOLUME 20A, JANUARY 1989 METALLURGICAL TRANSACTIONS A

Fig. 7--Scanning electron micrographs showing variation of fracture mode in Cr-Mo-V steel samples from (a) cold location-exposed at 288 ~
(b) Ring l--exposed at 454 ~ (c) hot location--exposed at 529 ~

predominantly intergranular (Figure 7(b)). The speci-

mens from both the cold and hot locations exhibited a
primarily transgranular cleavage mode. Typical Auger
spectra of the specimens from the cold location and Ring
1 are compared in Figure 8. The spectrum of the former
specimen represented matrix composition, since the
fracture mode was transgranular. In the latter specimen, a) C O L D L O C A T I O N
- TRANSGRANULAF
a considerable amount of phosphorus, molybdenum, and
carbon was noted on the grain boundaries. The average
phosphorous concentration on the grain boundary was
calculated to be 3.8 at. pct from the peak height ratio of
phosphorus to iron. The higher molybdenum and carbon Fe

peaks in the lower spectra (Figure 8) presumably are due

to presence of carbides on the grain boundaries. The tin
l
concentration on the grain boundaries was below the de-
tectable limit of the instrument. These results suggest
that embrittlement that occurred in service at Ring 6 lo-
cation was due to segregation of phosphorus alone to the b) R I N G 1
- INTERGRANULAR
grain boundaries.
2. 2.25Cr-1Mo steel
The results of impact properties of 2.25Cr-lMo steel
Fe ~-e
in the service-exposed and de-embrittled conditions are
summarized in Table VIII. The FATT and room tem-
perature, and upper shelf impact energies of the nozzle E (eV) ~.

chamber casting in the service-exposed condition were Fig. 8 - - A u g e r spectra of Cr-Mo-V samples from (a) cold location;
lower than those of both the flow guide and blade ring. (b) Ring 1.

METALLURGICAL TRANSACTIONS A VOLUME 20A, JANUARY 1989--93

 Table VIII. Impact Properties of 2.25Cr-lMo Cast Steels
Room
Exposure- Temperature
Temperature Impact Energy
Component ~ ~ Joules
Flow guide 454 850 22
Flow guide
de-embrittled -- -- 132
Blade ring 427 800 29
Nozzle chamber 538 1000 8 6
Nozzle chamber
de-embrittlement -- -- 27
Consistent with tensile ductility, these results suggest that
the toughness of the nozzle chamber casting decreased
as a result of service exposure. The blade ring which was
exposed at 427 ~ (800 ~ exhibited the highest tran-
sition temperature; however, the de-embrittling treat-
ment at 638 ~ (1180 ~ significantly lowered the FATI"
and increased the impact energy of the flow guide steel,
suggesting that the embrittlement that took place in
service was reversible. On the other hand, the de-
embrittling treatment slightly lowered the FATT of the
nozzle chamber steel from 82 ~ (180 ~ to 57 ~
(135 ~ Therefore, the embrittlement which occurred
in this steel during service was predominantly irrevers-
ible. Though the nozzle chamber was exposed at 538 ~
(1000 ~ and had softened significantly, the softening
did not improve impact toughness of this steel, as it did
in Cr-Mo-V steel.
The broken Charpy specimens machined from the flow
guide and blade ring in the service-exposed condition
exhibited intergranular fracture mode, while the one from
the nozzle chamber failed in cleavage and dimple modes
of fracture. As expected, the de-embrittling treatment
changed the fracture mode from intergranular to trans-
granular in the flow guide and blade ring steels. Typical
fractographs are shown in Figure 9. Auger spectrum ob-
tained from an intergranular fracture surface is compared
with the transgranular fracture of the specimen from the
nozzle chamber in Figure 10. The spectrum of the for-
mer fracture surface showed considerable amounts of
phosphorus and tin on the prior austenite grain bound-
aries. The calculated phosphorus and tin on the bound-
aries were 5.6 and 0.7 at. pct, respectively. These results
suggest that segregation of phosphorus and tin to the grain
boundaries in service was responsible for the observed
embrittlement of the flow guide and blade ring castings.
IV. D I S C U S S I O N
A. Softening
The results presented in the previous section demon-
strate that both Cr-Mo-V and 2 . 2 5 C r - l M o steel soften
when they are exposed at a temperature greater than 454 ~
(850 ~ Contrary to the observations of Zhe et al.,tl~
the results of this study show no appreciable softening
in the samples taken from Ring 1 after service exposure,
suggesting the minimum exposure temperature at which
9 4 - - V O L U M E 20A, J A N U A R Y 1989
Upper Shelf Upper Shelf
Temperature Energy 50 Pct FATT
Ft/Lbs ~ ~ Joules Ft/Lbs ~ ~
16 149 300 152 112 93 200
97 93 200 174 129 4 40
21 204 400 156 115 132 270
204 400 111 82 82 180
20 204 400 81 60 57 t35
the Cr-Mo-V rotor steel softens during service is signif-
icantly higher than what they have reported. The exis-
tence of minimum exposure temperature for softening to
occur during service is related to the higher tempering
temperatures normally used for these steels.
The main factors affecting the tensile and creep strengths
of a low alloy ferritic steel are the morphology and type
of carbides, and the amount of alloying elements present
in the ferrite. The carbide morphology and alloying ele-
ments in solid solution control movement of dislocations
in the ferrite grains. I2~ It has been suggested that the
creep strength of these steels decreases as the carbides
grow and lose coherency with the matrix, and is also
affected by the level of molybdenum content in the ma-
trix; t21,221 the strength is directly related to the molyb-
denum content. Williams and Wilshire I23~ have further
shown that the hardness of a 0.5Cr-0.5Mo-0.25V steel
before and after service at elevated temperatures de-
creases with increasing inter-carbide particle spacing and
with decreasing alloying elements in the solid solution.
Though the influence of service exposure on the micro-
structure is not evaluated in this study, there is evidence
in the literature to show that service exposure at elevated
temperatures of 454 ~ (850 ~ and above results in
coarsening of carbides, 123,24] spheroidization of car-
bides, E7,81an increase in inter-particle spacing, t231and pre-
cipitation of more stable carbides E3-24j in the Cr-Mo-V
and Cr-Mo type steels. Recent studies by several inves-
tigators [6,8,241 have shown service exposure causes pre-
cipitation of acicular carbide needles (M2C) and spherical
carbide particles (M6C) and H-type carbides. Precipita-
tion of these carbides during service depletes the alloy-
ing element content in the ferrite matrix. In fact, the
chemical analyses of the ferrite phase of service-exposed
Cr-Mo TMand Cr-Mo-V 161 steels have revealed a signifi-
cant decrease in molybdenum and carbon contents in sol-
id solution after service exposure. The observed softening
of Cr-Mo-V rotor steel and the 2.25Cr-lMo nozzle
chamber casting in this study can be attributed to changes
in microstructure and depletion of alloying elements in
solid solution that occurred in service. Since these mi-
crostructural changes are thermally activated processes,
the degree of softening is directly related to the service
temperature. From the present mechanical property re-
sults, it can be inferred that carbides produced during
the original high temperature tempering are extremely
stable during long-term service at temperatures up to
454 ~ (850 ~
M E T A L L U R G I C A L TRANSACTIONS A
Fig. 9--Fracture mode of 2.25Cr-lMo steel specimens from (a) the flow g u i d e - - a s service-exposed at 454 ~ (b) the flow guide service-exposed
and de-embrittled; (c) blade r i n g - - a s service-exposed at 427 ~ (d) nozzle chamber as service-exposed at 538 ~
B. Carbide-Induced Embrittlement
In contrast to the results for Cr-Mo-V steel, softening
of 2.25Cr-lMo steel is accompanied by a loss of duc-
tility and impact toughness. Since this toughness loss is
not fully recovered by the de-embrittling treatment, it is
reasonable to conclude that the loss is due to changes in
carbide type or morphology during service. It is not well
established what changes in carbide morphology cause
irreversible embrittlement. Brindley and Lindley ~4~have
shown that the tensile ductility of an iron-carbon alloy
decreases with increasing grain boundary plate cementite
particle size. They have further shown that cracking of
these platelet cementite particles is responsible for form-
ing cleavage microcracks in the ferrite. Such cleavage
cracks are not observed when the cementite is precipi-
tated inside the ferrite grain.
METALLURGICAL TRANSACTIONS A
A simple mass calculation indicates that the carbon
content of Cr-Mo-V steel is twice the amount that is
needed to precipitate all vanadium, molybdenum, and chro-
mium as their respective carbides, unlike in 2.25Cr-lMo
steel. This excess carbon is present in the former steel
as cementite, and, hence, it is reasonable to assume that
the Cr-Mo-V steel has a larger amount of grain boundary
cementite platelets than in the other steel. If coarsening
of grain boundary cementite platelets in service was an
important factor for the toughness loss, the Cr-Mo-V steel
should have also embrittled irreversibly as 2.25Cr-lMo
steel did in service, contrary to the results observed in
the present study.
Recent carbide extraction work by Bigs and Wada ~251
has revealed that service exposure causes precipitation
of M2C carbide needles in the ferrite grain, and spherical
M2C carbide particles on the prior austenite grain
VOLUME 20A, JANUARY 1989--95

a)-NTO
RZ
AZ
NLSEC
GH
RA
AMBL
NUEARR
~ e
T aries, while at the hot location the temperature is too
b)B LA
- IN DR
TEER
GIR
NA
GNULAR
E (eV)
Fig. 10--Auger spectra of service-exposed samples from (a) nozzle
chamber; (b) blade ring.
boundaries in 1Cr-0.5Mo steel. They have postulated that
the precipitation of these carbides lowers the impact
toughness of the steels. The precipitation of molybde-
num carbides (M2C) can occur during service in both Cr-
Mo-V and 2 . 2 5 C r - l M o steels, but the temperature at
which these carbides form and the kinetics of formation
are expected to be different for these steels. Qu and Kuo [6]
have suggested that the presence of vanadium decreases
the rate of formation of molybdenum-rich carbides and
favors the precipitation of M6C o v e r M2C during service
at 540 ~ (1004 ~ Their results have shown that pre-
cipitation and coarsening of molybdenum-rich carbides
(M6C) have a detrimental effect on impact toughness of
2.25Cr-lMo-0.4V steel. The present results, coupled with
the results of Qu and K u o , [61 indicate that Cr-Mo-V steel
is not susceptible to carbide-induced embrittlement dur-
ing service at a temperature below 540 ~
From the results of Bigs and Wada f251and Qu and Kuo, [61
it can be inferred that precipitation of molybdenum car-
bides (M2C or M6C ) during service is detrimental for the
toughness of Cr-Mo(V) type ferritic steels. However, the
mechanism by which carbides affect toughness is not
understood at this time. Hence, a systematic investiga-
tion of all the variables such as carbide type morphology
and distribution and service temperature is needed to un-
derstand the role of carbides on the toughness.
C. Temper Embrittlement
In both Cr-Mo-V and 2 . 2 5 C r - l M o steels, the most se-
vere temper embrittlement occurs in service when they
are exposed to a temperature near 427 ~ (800 ~ The
observation of a maxima in F A T T vs service temperature
for the Cr-Mo-V rotor steel (Figure 6) is consistent with
the findings of Hirota e t al. L13~and Zhe et al. tm~ The FATT
data coupled with fractography results (Figure 7) suggest
that the rotor steel does not appreciably temper embrittle
96--VOLUME 20A, JANUARY 1989
at 288 ~ (550 ~ and 529 ~ (985 ~ even after long-
term service exposure. The absence of intergranular
fracture in the Charpy specimens taken from the cold
and hot locations indicates that the grain boundaries are
not weakened by the segregation of impurities (partic-
ularly phosphorus for Cr-Mo-V steel) during service. At
the cold location, the service temperature is too low for
significant levels of impurities to diffuse to the bound-
high to build up a critical concentration of impurities
needed at the grain boundaries to weaken them. This type
of temperature dependency of embrittlement is normally
referred to as C-type behavior for reversible temper em-
brittlement, t26] Consistent with the present results, evi-
dence for the occurrence of severe embrittlement of
Ni-Cr-Mo-V steel at a temperature around 454 ~ (850 ~
can be found in the literature. [26,271
Results of past studies suggest that the original F A T T
and temper embrittlement behavior of a Cr-Mo-V rotor
steel are also a function of tensile strength of the steel. E1'151
It is clear from the data of the de-embrittled specimens
(Figure 6) that softening, which resulted from service
exposure, has slightly lowered the FATT of the steel.
The temper embrittlement susceptibility, as measured by
the difference in F A T T (A FATT) in the service-exposed
and de-embrittled conditions, tends to decrease with in-
creasing service temperature above 466 ~ (870 ~ The
difference is estimated to approach zero (Figure 6) at a
temperature of approximately 552 ~ (1025 ~
This A FATT actually represents a shift in FATT due
to service exposure and any change in FATT as a result
of slow cooling from the original tempering temperature.
As stated earlier, the rotor forgings are typically air cooled
from the austenitizing temperature and furnace cooled
from the tempering temperature during manufacturing,
and, thus, are slowly cooled through the critical tem-
perature range (300 to 550 ~ where reversible temper
embrittlement normally occurs. Due to the large diam-
eter of these forgings, the occurrence of some temper
embrittlement during cooling is unavoidable. The results
obtained on the Buck rotor rml have shown that the shift
in FATT due to slow cooling of the forging from the
original tempering treatment can be as high as 50 ~
(90 ~ Therefore, the observed difference in FATT in
the as-received and de-embrittled condition at the hot lo-
cation (Figure 6) is significantly ( ~ 2 0 ~ lower than the
F A T T shift expected as a result of slow cooling during
manufacturing. Hence, these results suggest that service
exposure at 530 ~ (985 ~ or above negates any det-
rimental effects of slow cooling through the critical tem-
perature range during the original heat treatment by
desegregating the phosphorus from the grain boundaries
in service. In fact, the occurrence of de-embrittlement
during service was confirmed by performing additional
Charpy tests on the specimens from the coupling loca-
tion of the rotor where service temperature was 80 ~
(175 ~ The FATT of the hot location is 22 ~ (40 ~
lower than that of the coupling location of the rotor.
Additions of molybdenum up to 0.7 pct is known to
reduce temper embrittlement susceptibility of 2.25Cr-Mo
type steel321 Molybdenum suppresses embrittlement by
scavenging phosphorus through the formation of a
METALLURGICAL TRANSACTIONS A
Mo-P compound and thus decreases phosphorus segrega-
tion to the grain boundaries, t2,281 McMahon and his co-
workers t3,1~ and Qu and Kuo ~6~ have s h o w n that
any decrease in molybdenum content in the matrix
due to formation of molybdenum carbides (MzC or M6C)
during tempering or aging significantly enhances em-
brittlement susceptibility of 2 . 2 5 C r - l M o and Cr-Mo-V
steels. Though service exposure has resulted in a de-
crease of molybdenum content in the matrix (as evi-
denced by softening), the observation of no enhancement
in temper embritflement susceptibility at the hot location
also indicates that the rotor steel does de-embrittle
during service at this temperature to negate the
phosphorus scavenging effect.
V. C O N C L U S I O N S
The influence of service temperature on softening and
embrittlement behavior of Cr-Mo-V and 2.25Cr-lMo steel
has been studied. From the results of this study the fol-
lowing conclusions can be drawn:
1. Both Cr-Mo-V and 2 . 2 5 C r - l M o steels soften only
when they are exposed at a temperature greater than
454 ~ (850 ~ The degree of softening of Cr-Mo-V
increases with increase in service temperature above
454 ~ (850 ~ In this case, the softening is accom-
panied with an improvement in tensile and creep duc-
tility and upper shelf energy.
2. The 2 . 2 5 C r - l M o steel has softened after service
exposure to 538 ~ (1000 ~ In addition to soften-
ing, service exposure at 538 ~ (1000 ~ results in
a decrease in tensile ductility and toughness of this
steel. This loss in toughness is in part irreversible and
is due to changes in carbide type or morphology dur-
ing service.
3. The Cr-Mo-V steel does not show any evidence of
carbide-induced irreversible embrittlement after long-
term exposure at 529 ~ (985 ~ The present results,
coupled with the results reported in the literature, in-
dicate that there is a critical service temperature
(540 ~ for Cr-Mo-V steel to embrittle due to changes
in carbide morphology or type in service.
4. The notch rupture life o f Cr-Mo-V steel is not im-
proved by softening as a result of service exposure.
5. Service exposure at 538 ~ (1000 ~ has lowered the
creep rupture life o f 2 . 2 5 C r - l M o steel by an order of
magnitude as compared to that of the steel exposed
at 454 ~ (850 ~
6 . Both steels severely temper embrittle during service
at a temperature around 427 ~ (800 ~ This em-
brittlement is due to segregation o f residual elements
to the grain boundaries in service.
7. The Cr-Mo-V steel does not temper embrittle during
service at 529 ~ (985 ~ It appears that service ex-
posure at this temperature can negate any detrimental
effects of slow cooling through the critical tempera-
ture range for temper embrittlement during original
heat treatment of the forging.
METALLURGICAL TRANSACTIONS A
ACKNOWLEDGMENTS
The author wishes to express sincere thanks to Drs.
R.L. Novak, B.B. Seth, B. Shaw, and T. Wada for crit-
ically reviewing the manuscript and giving constructive
comments.
REFERENCES
1. R. Viswanathan and A. Joshi: Metall. Trans. A, 1975, vol. 6A,
pp. 2289-97.
2. T.' Wada and W.C. Hagel: Metall. Trans. A, 1976, vol. 7A,
pp. 1419-26.
3. J. Yu and C.J. McMahon, Jr.: MetaU. Trans. A, 1980, vol. l l A ,
pp. 277-89.
4. B.J. Brindley and T.C. Lindley: J. Iron and Steel lnst., 1972,
vol. 23, pp. 124-25.
5. Y. Nishizaka, Y. Hara, A. Hori, T. Tsukahara, K. Miyano,
T. Wada, and T.B. Cox: ASME Proc. Pressure Vessel Piping
Conf., 1985, PVP-vol. 98-1, pp. 125-35.
6. Z. Qu and K.H. Kuo: Metall. Trans. A, 1981, vol. 12A,
pp. 1333-37.
7. T. Wada and V.A. Bigs: Metall. Trans. A, 1983, vol. 14A,
pp. 845-55.
8. L.H. Toft and R.A. Marsden: J1SI & JIM Proc. Intl. Conf. on
Structural Process in Creep, 1963, pp. 276-93.
9. N.S. Cheruvu: ASM Proc. Intl. Conf. on Nuclear Power Plant
Aging, Availability Factor and Reliability Analysis, V.S. Goel,
ed., 1985, pp. 575-80.
10. O. Zhe, S.C. Fu, and C.J. McMahon, Jr.: EPRIReport CS2242,
Project 559, February 1982.
11. N.S. Cheruvu, W.E. Howard, and O.M. Beasley: ASME Joint
Power Generation Conf., paper #85-JPGC-Pwr-29, 1985.
12. H.C. Argo and B.B. Seth: Case Studies in Fracture Mechanics,
Army Materials Research Center, MS77-5, T.P. Rich and D.J.
Cartwright, eds., 1977, pp. 3.2.1-11.
13. Y. Hirota, Y. Kadoya, T. Goto, M. Wake, and H. Fuji:
Mitsubishi Heavy Industries Ltd. Technical Review, October 1982.
14. Supplemental Report on The Elevated Temperature Properties of
Cr-Mo Steels, ASTM Data Services Publications No. DS6S1,
American Society for Testing and Materials, J.A. Van Etho and
W.F. Simmons, eds., 1966, p. 52.
15. L. Tu and B.B. Seth: Metall. Tech., 1978, vol. 5, pp. 79-91.
16. R.V. Hart: Metall. Tech., 1976, vol. 3, pp. 1-7.
17. N.S. Cheruvu and L.R. Malmfeldt: ASME Joint Power Gener-
ation Conf., paper #87-JPGC-Pwr-53, 1987.
18. R. Viswanathan and J.I. Jaffee: Turbine Rotor Life Assessment
and Improvement, EEl Prime Movers Committee, paper R9,
Miami, FL, 1984.
19. R. Viswanathan: Metall. Tech., 1974, vol. 1, pp. 283-88.
20. J. Nutting: A1ME Proc. Topical Conference of Ferritic Alloys for
Use in the Nuclear Energy Technologies, J.W. Davis and D.J.
Michel, eds., 1983, pp. 3-16.
21. J.D. Murray: in Precipitation Process in Steels, ISI Special Re-
port no. 64, 1959, p. 285.
22: J.D. Baird, A. Jamieson, R.R. Peterson, and R.C. Cochrane:
Proc. Conf. on The Creep Strength in Steel and High Temper-
ature Alloys, Sheffield, Metals Society, London, 1973,
pp. 207-15.
23. K.R. Williams and B. Wilshire: Materials Sci. Eng., 1981,
vol. 47, pp. 151-60.
24. K.R. Williams and B. Wilshire: Materials Sci. and Eng., 1977,
vol. 28, pp. 289-96.
25. V.A. Biss and T. Wada: Metall. Trans. A, 1985, vol. 16A,
pp. 109-14.
26. G.C. Gould: American Society for Testing and Materials, Spec.
Tech. Publication 407, 1968, pp. 90-105.
27. R. Viswanathan and T.P. Sherlock: Metall. Trans., 1972,
vol. 3, pp. 459-68.
28. C.J. McMahon, A.K. Cianelli, and H.C. Feng: Metall. Trans.
A, 1977, vol. 8A, pp. 1055-61.
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