DEVELOPMENT OF MODIFIED 9 Cr-1 Mo STEEL FOR ELEVATED-TEMPERATURE SERVICE*

Vlnod K. Sikka
Metals and Ceramics Division COHF-8306 59—16
Oak Ridge National Laboratory
Oak Ridge, TN 37830
DEB4 003161

The status of development and commercialization Table I. Chemical analysis of modified

of a modified 9 Cr-1 Mo alloy is presented. The alloy 9 Cr-1 Mo steel and its comparison
is modified by the addition of 0.06 to 0.10% Nb and with standard 9 Cr-1 Mo steel
0.18 to 0.25Z V. The alloy is recommended for use in
the normalized and tempered condition (1040°C for 1 h,
air cooled to room temperature; 760°C for 1 h, air Content range, wt 7.
cooled to room temperature). Heat treatment, Charpy
Impact, tensile, and creep properties of the alloy are Element Modified Standard
described in detail along with a brief description of 9 Cr-1 Mo 9 Cr-1 Mo
other properties. (Grade 91) (Grade 9)

The modified alloy has creep strength that Carbon 0.08-O.12 0.15 max
exceeds that of standard 9 Cr-1 Mo and 2 1/4 Cr-1 Mo Manganese 0.30-0.60 0.30-0.60
steels for the temperature range from 427 to 704°C. Phosphorus 0.020 max 0.030 max
The total-elongation and reductlon-of-area values for Sulfur 0.010 max 0.030 max
all test temperatures and rupture times up to 22,500 h Silicon O.2O-O.5O 1.00 max
exceed 15 and 70Z, respectively. The estimated design Chromium 8.00-9.50 8.00-10.00
allowable stresses for this alloy are higher than Molybdenum 0.85-1.05 0.90-1.10
those for standard 9 Cr-1 Mo and 2 1/4 Cr-1 Mo steel. Nickel 0.40 max
At 550°C and above, these values are twice those of Vanadium 0.18-0.25
the other alloys. Operating experience on this alloy Niobium 0.06-0.10
is being obtained by installing tubes in various steam Nitrogen 0.030-0.070
power plants. Aluminum 0.04 max

1. Introduction
Both niobium and vanadium are added to the alloy
A 9 Cr-1 Mo steel with properties improved over to improve its elevated-temperature strength
the 2 1/4 Cr-1 Mo steel and that of other ferritics in properties. Microstructural work has indicated that
the ranges from 9 to 122 Cr and 1 to 2% Mo has been the improved strength of the modified alloy comes from
developed recently (1,2). The development of this two factors. First, fine M 2 3C 6 precipitate particles
alloy was funded jointly by the U.S. Department of nucleate on Nb(C,N), which first appears during the
Energy fossil energy and breeder reactor development heat treatment. Second, the vanadium enters M 2 3C 6 and
programs. The purpose of this paper is to describe retards its growth at the service temperature. The
the status of this development, with special emphasis finer distribution of M 2 3C 6 adds to the strength, and •
on the status of approval of this material in the its retarded growth holds the strength for long
ASTM specifications and the ASME Boiler and Pressure periods of time at the service temperature.
Vessel Code.

3. Heat Treatment
2. Chemical Specifications
The alloy is recommended for use in the normal-
The composition specifications of modified ized and tempered condition. The normalizing treat-
9 Cr-1 Mo steel are listed in Table I and compared ment consists of heating the alloy to 1040°C, holding
with those of standard 9 Cr-1 Mo steel. The main for 1 h for material up to 25-mm thick, and then air
difference of the modified alloy when compared with cooling to room temperature. This treatment produces
the standard alloy include (1) an addition of niobium a fully martensitic structure. The typical hardness
and vanadium, (2) a specified range for each element, in this condition is Rockwell C40. The tempering
and (3) a specification for nitrogen, which is not treatment consists of heating the normalized steel
listed for the standard 9 Cr-1 Mo. to 760°C, holding for 1 h up to a 25-mm thickness,

Research sponsored by the Office of Fossil Energy and the Office of Breeder Reactor Technology Project,
U.S. Department of Energy, under contract W-7405-eng-26 with Union Carbide Corporation.

MASTER
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 and then air cooling to room temperature. The typical The tempering response of the alloy can be
hardness in this condition is Rockwell >!.l>5. Optical described by the Holloraon-Jaffe (HJ) tempering
and transmission electron micrographs of Lerapered parameter. This parameter is given by
marte-w'-:• -ire shown in Figures 1 and 2. Figure 1
oiio.. .p.e diiuj -- single pnase (.free from HJ = T(C + log t) (1)
6-ferrite; and has a fine grain size (ASTM 8-9). The
transmission electron micrograph shows that the tem- where
pered microstructure has high-dislocation-density sub-
boundaries in the matrix. The subboundaries are temperature in k,
stabilized by the precipitation of carbides on them. time in hours,
Carbides also precipitate at the prior austenite grain HJ constant.
boundaries.
The optimized value of C for two commercial heats
(30176 and 30394) characterized to date was determined
to be 22.3.

The correlation of tempering parameter with

hardness, Charpy V-notch energy, 0.2X yield strength,
and total elongation at room temperature is shown in
Figure 3. The 0.22 yield and ultimate tensile
strengths are well correlated with room-temperature
hardness (Figure 4 ) . Such correlations are useful
when the material must meet both the tensile property
and hardness criteria.

The grain coarsening response of the alloy was

examined as a function of the normalizing temperature
and time (Figure 5 ) . Grain coarsening of the modified
alloy occurred only when the normalizing temperature
was increased about 100°C or more above the specified
normalizing temperature of 1040"C. Even in the
Figure 1 — Typical mlcrostructure of modified coarsened condition, the grain size for the modified
9 Cr-1 Mo steel after the nominal normalizing and alloy remained near ASTM No. 5.
tempering treatment (1040°C for 1 h; 760°C for 1 h ) .
Note that the grain size is very fine.
4. Commercial Melting and Fabrication

Eight heats of this alloy have been melted by

commercial vendors (Table II). A summary of infor-
mation on the fabrication of this alloy by the commer-
cial vendors is given la Table III. The overall
consensus is that melting and fabrication of this
alloy presents no technical problems, although costs
will obviously vary depending upon the melting and
fabrication process selected.

5. Mechanical Properties

The main emphasis on the mechanical properties

of the alloy was limited to Charpy impact and tensile
testing. Each of these properties is described
here briefly.

5.1 Charpy-Impact Properties

The curves of Charpy V-notch impact energy versus

test temperature for two commercial heats of modified
9 Cr-1 Mo steel *"e compared with a heat of standard
9 Cr-1 Mo steel "igure 6. All tests were conducted
on specimens with t.he V-notch parallel to the rolling
direction. The standard 9 Cr-1 Mo heat was electric
furnace melted. One modified 9 Cr-1 Mo steel heat was
melted by both the argon-oxygen decarburization (AOD)
and AOD-ESR combination. All of the second heat of
"^ J«i modified 9 Cr-1 Mo was melted by the AOD-ESR process.
Data In this figure show that the 68-J (50-ft-lb)
Figure 2 — Transmission electron micrograph of a ductlle-to-brittle transition temperatures for both
specimen normalized at 1040°C for 1 h and tempered at heats of modified 9 Cr-1 Mo are lower than that for
760°C for 1 h. The micrograph shows that tempered the standard 9 Cr-1 Mo heat. The upper-shelf energies
martenslte consists of dislocation substructure and for the AOD-ESR-melted modified 9 Cr-1 Mo heats are
carbides (M 2 3C 6 and MC) on both the grain and eubgrain much higher than those for either AOD-melted modified
boundaries• 9 Cr-1 Mo steel or electric-furnace-melted standard
 U10 3 ) i
I T II" I
TEST TEMPERATURE = ROOM TEMPERATURE TEMPERING rEMPERATURE 1°CI
O - 732 V - 774
- 25.0 A - 746 Q ~ 788
D - 760 £>- 816
OPE?; SYMBOLS - HEAT 30394
CLOSED SYMBOLS - HEAT 30(76
24.0

23.0

9EST FIT
•O- C^* BEST FIT

80 84 88 92 96 80 160 240 400 500 600 700 10 20 30 40

HARDNES5 (ROCKWELL B l CHARPY V-NOTCH ENERGY (J) 0 . 2 % YIELD STRENGTH <MPo) TOTAL ELONGATION (%)

Figure 3 — Tempering parameter as a function of hardness, Charpy energy, 0.2% yield strength, and total elongation
at room temperature.

HARDNESS (ROCKWELL C) HARCNESS (ROCKWELLC»

8 10 12 14 16 '8 20 10 12 14 16 16 29
1 ! ! 1 1 1 1
MODIFIED 9Cr-«Mo STEEL
O - H E A T 30176
A - HEAT 30394
NORMALIZED: 1040 °C. 1h
TEMPERED: 732-816°C. O.25-16.OH

! i
- I ?oo 5
100 j 2
! UJ
- ! 650 £
! </>
UJ
6 0 0
~ ! ^

550 •"

£ 500 | ,
^ 70 — MODIFIED 9 C r - ( M o STEEL
O - H E A T 30176 3 :
A - H E A T 30394 450
NORMALIZED: 1040 "C . 1h
TEMPERED: 752-BI6 "C. 0 . 2 5 - 16.01 400

350
90 92 94 96 90 32 94 96
(a). HARDNESS (ROCKWELL B) (b) HARDNESS (ROCKWELL B)

Figure 4 —Room-temperature strength versus hardness for two commercial heats of modified 9 Cr-1 Mo steel,
(a) Yield. (b) Ultimate.

11850) 1)9001 11950) 12000) 12050)

OlO 1038 1065 1093 1121
TEMPERATURE •CIT) FOR 8 n MOLD
- 61
_ 15 — NORMALIZING TEMPERATURE °C I " F I
E 6 "
3. 0 - 927(1700) V-103811900'
~ 40 6 i
A - 9 5 1 117501 a- 1065 1(950:
D - 992 (18001 0-1093(2000)
~ O - 1 0 1 0 (18501 6-1121(2050!
I

S
a 25 -
S 7.5 g
I 20 CO ^^
o 80 £
3 0 _ as ^
^ ^ ^ ^
~~ A --^•" 9.0
-1 95
15
o 10.0
10 (18501 (19001 (1950) (20001 (20501
1010 1038 IC65 1093
1
1121
I I '
5 TEMPERATURE "C ."1 FOR 111 HOLO
I I I I 1 1 1 1 ! I 1 1 1 1
26.6 270 271 278 232 286 290 29.4 238 302 306 310 31.1 ^.8 3£2 326 ( x i o 3 )
H.' - T (22.3 • log I )

Figure 5 — Grain coarsening behavior of modified 9 Cr-1 Mo steel.

 Table II. List of commercial heats melted on
modified 9 Cr-1 Mo steel

Heat size
Heat Melter Melting practice8
(tons)

F5349 Quaker 4 A0D

30383 CarTech 15 AOD
30394b CarTech 15 AOD/ESR
30176 c CarTech 15 AOD/ESR
30182 c CarTech 15 AOD/ESR
lO148d Electralloy 15 AOD and AOD/ESR
XA3602 Combustion 0.5 Air induction
Engineering
91887 CarTech 2.5 Electric/ESR
YYC982C Sumitomo, Japan 2.0 Vacuum Induction
59020 NKK, Japan 5.0 Vacuum Induction

a
AOD » argon-oxygen decarburization. ESR » electroslag
remelting.
b
Heat 303S4 is half of.heat 30383 and was electroslag
remelted.
c
Heats 30176 and 30182 are the same heat. Their numbers
are different because CarTech identifies ingots separately.
d
Heat 10148 was melted by AOD process. Half this heat
was subsequently electroslag remelted.

Table III. Summary of information on fabrication of commercial heats of modified 9 Cr-1 Mo alloy

Product size, mm
Melting
Heat Melter Product Fabrication method Fabricator
practicea
OD Thickness

F5349 Quaker AOD Plate 16 Hot forged, hot rolled ORNL, Y-12
30383 CarTech AOD Plate 51 Hot forged, hot rolled Jessop
30383 CarTech AOD Bar 95 Hot forged, hot rolled CarTech
30383 CarTech AOD Tube 102 15 Hot extruded Amax
30394 CarTech AOD-ESR Plate 25 Hot forged, hot rolled Jessop
30394 CarTech AOD-ESR Bar 232 Hot forged CarTech
30394 CarTech AOD-ESR Tube 102 15 Hot extruded Amax
30394 CarTech AOD-ESR Tube 76 13 Hot rotary pierced Timken
30182 CarTach AOD-ESR Plate 16 Hot forged, hot rolled CE
30182 CarTech AOD-ESR Bar 232 Hot forged CarTech
30182 CarTech AOD-ESR Tube 102 15 Hot extruded Amax
30182 CarTech AOD-ESR Tube 76 13 Hot rotary pierced Timken
30176 CarTech AOD-ESR Plate 25 Hot forged, hot rolled Jessop
10148 Elactralloy AOD Plate 16 Hot forged, tempered. ORNL
cold rolled
10148 Electralloy AOD Bar 44 Hot extruded ORNL
10148 Electralloy AOD Bar 107 Hot rolled Bethlehem
10148 Electralloy AOD Pipe 245 25 Hot pilgered Phoenix
10148 Electralloy/ AOD-ESR Plate 203 Hot rolled Universal
Universal Cyclops Cyclops
10148 Electralloy/ AOD-ESR Plate 51 Hot rolled Universal
Universal Cyclops Cyclops
10148 Electralloy/ AOD-ESR Octagon 200 Hot forged Universal
Universal Cyclops box Cyclops
10148 Electralloy/ AOD-ESR Round 232 Hot forged Universal
Universal Cyclops Cyclops
10148 Electralloy/ AOD-ESR Tube 54 9.45 Hot extruded, cold TI Stainless
Universal Cyclops reduced (UK)
XA3602 Combustion Air induc- Tube 51 8.03 Centrifugally cast and CE
Engineering tion cold pilgered
YYC982C Sumitomo VIM Tube 76 13 Hot extruded, cold drawn sumitomo
YYC982C Sumitomo VIM Tube 51 6.4 Hot extruded, cold drawn Sumitomo
59020 NKK VIM Plate 25 Hot forged, hot rolled NKK
59020 NKK VIM Tube 76 13 Hot extruded, cold drawn NKK
59020 NKK VIM Tube 51 6.4 Hot extruded, cold drawn NKK
a
A0D » argon-oxygen decarburization, ESR » electroslag remelting, VIM » vacuum induction melting.
 1. Melting practice, AOD versus AOD-ESR, had no
1 i 1 1 1 1 ! effect on tensile properties for test temperatures up
to 760°C. This is different from impact prooerties,
^—0.5T. Si ESR
which were far superior for AOD-ESR-melted material to
those for AOD-melted material.
0.2% 5 ESfl
-r,r ^ — 0.5V. s. AOD
2. The tensile properties of modified 9 Cr-1 Mo
steel are sensitive to strain rate at room temperature
and threo higher test temperatures: 427, 533, and
649°C. The yield and ultimate tensile strengths
decrease some with decreasing strain rate at room tem-

//
' /
/ . 0.6V. Si
STANDARD 9 C - ) Wo
perature. This occurs without any change in ductility.
At 427 and 538°C, strength decreases and ductility
increases with decreasing strain rate. Strength
/

. ^
y
1 1 1 |
WR ORIENTATION

1 1
decreases with some decrease in ductility at 649°C.

50 )00 (50 200 250 300 3. A decrease of 14 to 28°C in tempering tem-

TEST TEMPERATURE 1'CI
perature from 760°C substantially increased yield and
ultimate tensile strengths for test temperatures
Figure 6 — Effect of melting process on the Charpy through 427°C. At a test temperature of 649°C, the
V-notch toughness from two 14-Mg (15-ton) commercial increase in strength was relatively small. Ductility
ESR heats of modified 9 Cr-1 Mo steel and one standard was only slightly affected by this drop in tempering
9 Cr-1 Mo steel plate. temperature. Changes in hardness and Charpy-impact
energy, as a result of change in tempering tempera-
ture, are shown in Figure 3.
9 Cr-1 Mo steel. This figure also shows that Charpy
properties are affected by both the silicon content 4. Tensile tests were conducted at room tem-
and the melting practice (3). The lower silicon con- perature and at the aging temperature on a single heat
tent or electroslag reuniting of the material produces (F5349) aged for 5000 and 11,600 h at 538, 593, and
lower transition temperatures and higher upper-shelf 649°C. Only small changes were observed in properties
energies. However, between the two factors, melting as a result of this treatment.
practice appears to have a much more potent effect
than silicon content.
5.3 Creep Data

5.2 Tensile Properties A substantial number of creep tests on the

commercial heats of modified 9 Cr-1 Mo steel are
Tensile properties of commercial heats of either ruptured or in progress. These tests are
modified 9 Cr-1 Mo steel have been measured for test being run at 427, 454, 482, 538, 593, 649, 677, and
temperatures from room temperature to 760°C. Data 704°C. Creep rupture data at 593°C on commercial
include the effects of melting practice, compositional heats of modified 9 Cr-1 Mo steel are plotted in
differences, strain rate (8.0-0.00008/oln), postweld Figure 9. Data in this figure are compared with the
heat treatment (1—112 h at 732°C), isothermal average curves for the modified 9 Cr-A Mo, standard
annealing treatment (1038°C for 1 h, fast cool to British 9 Cr-1 Mo, standard American 9 Cr-1 Mo, and
704°C, and hold for 14 h followed, by air cooling), and 2 1/4 Cr-1 Mo steels, the modified and standard
thermal aging treatment (5000 and 11,600 h at 538, British 9 Cr-1 Mo sf:.eels are both tested in the
593, and 649 •-. normalized and tempered condition. The standard
American 9 Cr-1 Mo and 2 1/4 Cr-1 Mo steels were
Typical plots of 0.2% yield and ultimate tensile tested in the annealed condition. The following
strengths against test temperature are shown in observations are derived from Figure 9.
Figure 7. Similar plots for total elongation and
reduction of area are shown in Figure 8. These plots I. The modified 9 Cr-1 Mo steel is significantly
combine data on plate, tube, and bar. All tests were stronger than standard 9 Cr-1 Mo and 2 1/4 Cr-1 Mo.
at a nominal strain rate of 0.004/min. Room- The strength difference becomes even more important
temperature data on individual product forms were used for rupture times exceeding 1000 h.
to determine the average values, the standard devia-
tion in the room-temperature data, and the recommended 2o Changing the heat treatment condition from
minimum properties for use in ASTM specifications. annealed to normalized and tempered improves the
These values are listed in Table IV, and the recom- creep-rupture strength only a small amount. However,
mended minimum values are the same for all three for the same heat treatment (normalizing and
products. The best fit average and minimum curves tempering) the composition modification made in our
based on the room-temperature specified minimum prop- alloy produced a very large improvement in creep-
erties (see Table IV) are also included in Figures 7 rupture strength.
and 8. These plots show that the minimum specified
properties at room temperature are conservative enough Figure 9 compares rupture strength only at 593°C.
to include data on all commercial heats through test The 105-h creep-rupture strength at temperatures from
temperatures of 760°C. 427 to 732°C is compared for various alloys in
Figure 10. This figure also includes the curve for
Tensile data analysis also showed the following 2 1/4 Cr-1 Mo steel tested in the normalized and tem-
features. pered condition. This figure shows again that the
 Modified 9Cr-lMo Steel Modified 9Cr-lMo Steel

Best Fit
a, Minimum

200 400 600 800 200 400 600 800

Temperature (°C) Temperature (°C)
Figure 7 — Plots of (a) 0.2% offset yield strength and (b) ultimate tensile strength as functions of test
temperature for plate, bar, and tube of commercial heats of modified 9 Cr-1 Mo steel. The best fit average and
minimum curves based on room-temperature specified minimum yield and ultimate tensile strength of 414 and 536 MPa
are included also in these figures.

Modified 9Cr-lMo Steel Modified 9Cr-iMo Steel

300 400 600 800 200 400 600 800

Temperature (°C) Temperature (°C)

Figure 8 — Plots of (a) total elongation and (b) reduction of are* as functions of test temperature for plate,
bar, and tube of commercial heats of modified 9 Cr-1 Mo steel. The best fit average and minimum curves based on
the room-temperature specified minimum total elongation and reduction of area of 18 and 552 are included also in
these figures.
 Table IV. Minimum tensile properties at room temperature specified
for various products of modified 9 Cr-1 Mo steel tested
in the normalized and tempered condition3

Strength, MPa Total Reduction

Product Calculate elongation of area
0.2% Ultimate (%)
a)
Plate Average 545 683 24.7 69.8
Average — 2SD 496 634 20.6 61.6
Average — 3SD 476 607 18.5 57.5
Recommended min 414 586 18 55

Tube Average 524 669 27 74

Average — 2SD 483 627 23 71
Average — 3SD 462 607 21 70
Recommended rain 414 586 18 55

Bar Average 531 676 28 73

Average — 2SD 469 614 26 70
Average — 3SD 434 586 25.5 68
Recommended min 414 586 18 55

a
At 1038°C for 1 h, air cooled to room temperature, and at 760°C
for 1 h, air cooled to room temperature.

BRITISH COMMERCIAL 9 C r - ( M o
(NORMALIZED AND TEMPEREDI
! 1 1 1| 1 1 1 1| 1 1 1 1| 1 I I 1i i i i i
; AVG
400 ~ 1 Moi N i : H V U —
2 1/4 O ~ 1 Mo: A ; AVG
- STANDARD 9 C r - 1 M o ; A; AVG

200 _ -
MODIFIED 9 C r - I M o
(NORMALIZED AND TEMPERED)

100 _

s 80 - HE«T MELTEB PROCESS ~ ^ ~

— 6 0 I A0 -- F3 05 (38429 TUAKER
CARTECH
AOD
AOD/ESR ^ ^ '
D - 3 0 1 7 6 CARTECH AOD/ESR
40
-o — 30383
-30394
CWTECH
CARTECH
AOO
AOD/ESR
- 1 0 1 4 8 ELECTRALLOY AOD
-91887 CARTECH ESR
> ••INDICATES TEST IN PROGRESS _
20 2 1/4 Cr - I Mo
TEST TEMPERATURE • 593"C ((100 V) (NORMALIZED AND TEMPERED;
N l • NORMALIZED AND TEMPERED
A • ANNEALED
| 1 1 ll 1 1 1 11 1 1 1 11 1 i 11 1 I i f !

TIME TO RUPTURE l h >

TYPE 3 0 4 SS

Figure 9 — Stress-rupture plot at 593°C comparing

data on commercial heats of modified 9 Cr-1 Mo steel 2 1/4 Cr - 1 Mo
(tested in normalized and tempered condition) with the ( ANNEALED)

average curves for the standard British 9 Cr-1 Mo

steel tested in the normalized and tempered condition
and standard American 9 Cr-1 Mo steel and 2 1/4 Cr-
1 Mo steel tested in the annealed condition.

400 450 500 550 GOO 650 700 750 8O0 S5O
TEMPERATURE <*C)

Figure 10 — Variation of 105-h creep rupture strength

with temperature for several materials.
 modified 9 Cr-1 Mo alloy is stronger than standard for 2 1/4 Cr-1 Mo (annealed and normalized and tempered)
9 Cr-1 Mo and 2 1/4 Cr-1 Mo steel for the entire tem- and standard 9 Cr-1 Mo steel (normalized and tempered)
perature range. The strength differences become more in Figure 12. This figure shows that the design
significant for temperatures exceeding 500°C. allowable stresses for the modified alloy are higher
than those of standard 9 Cr-1 Mo and 2 1/4 Cr-1 Mo
There is some concern ;/lth the associated loss steels for the entire temperature range. Furthermore,
in ductility when the creep strength of an alloy is the design allowable stresses become approximately
increased. The total elongation and reduction of area twice those of the other alloys at 55O°C and above.
for creep tests ruptured thus far on the commercial
*-•• - ifled 9 Cr-1 Mo steel are plotted in
ISO
Fift^. . The total elongation for most heats exceed i i r
152, and the reduction of area exceeds 70S. Further-
more, these data show no indication of drop in 140
ductility with Increasing rupture time. This is true
for all test temperatures. 130 - 2 1/4 O - ' Mo
(NORMALIZED AND TEMPERED)
120
The data presented above show that the alloy we
have developed has high creep strength and excellent
| 110
creep ductility. MOOIFiED 9 C r - >Mo
!NORMALI2ED AND TEMPERED I
5 '00
5.4 Estimated Design Allowable Stresses z
z 90
Tensile and creep data were employed to estimate
the design allowable stresses for the modified i/i
9 Cr-1 Mo steel. The procedure employed for these £ eo
in
estimates was the one used for the ASME Code,
^ 70
Sect. VIII. The maximum design allowable stresses CD
<X
estimated for the modified 9 Cr-1 Mo steel *
(normalized and tempered) are compared with those O 60

30

20
BRITISH COMMERCIAL 9 C r - < M o
40 j - (NORMALIZED AND TEMPERED J -
I 10

3O
1
350 400 450 500 550 600 650 700 750 800
TEMPERATURE {"C J
g 20
e Figure 12 — Estimated design allowable stresses as a
(0 function of temperature for modified 9 Cr-1 Mo steel.
Design allowable stress values for standard 9 Cr-1 Mo
0 I I I LjJ I I LjJ L_ and 2 1/4 Cr-1 Mo steel are also included for
comparison.

6. Related Properties

Data on both physical and mechanical properties

other than these presented in this paper are either
available or being collected in an effort to com-
pletely characterize the modified 9 Cr-1 Mo alloy.
HEATS
F5349 Each of these properties is listed with its status
30182 described briefly.
30176
TEST 30383
TEMPERATURES [*C I 30391
0-482 0-649 10148 6.1 Physical Properties
A - 538 a- 677 91887
•-593 y-704 XA36O3
In this area, effort is under way to determine
i I i i
the thermal expansion coefficient, thermal conduc-
10° tivity, and heat capacity of one heat each of standard
TIME TO RUPTURE I and modified 9 Cr-1 Mo alloy. The objective of the
study is to determine if there are significant dif-
Figure 11 Plots of total elongation (top) and ferences in the physical properties of the two alloys.
reduction of area (bottom) functions of rupture time
for commercial heats of modified 9 Cr-1 Mo steel Results of this study have shown that the thermal
tested in the normalized and tempered condition. Data expansion coefficient of modified 9 Cr-I Mo steel is
are for test temperatures in the range 482 to 704°C the same for that observed in this study and reported
and for eight commercial heats. in the literature for the standard 9 Cr-1 Mo steel (4).
 However, the thermal conductivity was found to be Air oxidation data at 593°C were obtained on both
related to the silicon content. Higher silicon the modified 9 Cr-1 Mo and 2 i/4 Cr-1 Mo steel for a
content tended to be associated with lower thermal period of 20,000 h. These data showed that the weight
conductivity. We have nested modified 9 Cr-1 Mo heats gain for 2 1/4 Cr-1 Mo steel vas about eight times
containing 0.2 and 0.5* Si and recommend that the that observed for the modified 9 Cr-1 Mo alloy. Tests
average values for these two heats be used as typical are now continuing to measure the weight gain for
values. longer periods.

6.2 Fatigue and Creep-Fatigue Tests 6.5

These tests are in progress at Oak Ridge National The weldability of modified 9 Cr-1 Mo steel is
Laboratory, Sandia National Laboratory, Northwestern being investigated with the Varestraint hot cracking
University, and the University of Connecticut. Data test, Battelie under-bead cracking test, Tekken
available have shown that the modified alloy has about Y-groove test, hydrogen sensitivity test, and stress-
the same fatigue strength (total strain range versus relief cracking test. Results available thus far have
number of cycles to failure) as type 316 stainless shown that the material is free from hot cracking
steel in the range from 525 to 593°C. The alloy also susceptibility, a preheat temperature of 200°C can
has superior fatigue life beyond 10 s cycles to prevent hydrogen sensitivity, and there are no stress-
2 1/4 Cr-1 Mo, standard 9 Cr-1 Mo, and type 304 relief cracking problems for a postweld heat-treatment
stainless steel. Microstructural observations on temperature of 732°C. The filler wire composition for
fatigue-tested specimens are reported by Jones (5). gas tungsten arc welding, electrode composition for
shielded metal arc welding, and the combination of
filler wire and flux for submerged arc welding are
6.3 Fatigue Crack Growth and Fracture Toughness currently being optimized to satisfy the strength and
ductility criteria set for the alloy.
These tests are currently in progress at the
Hanford Engineering Development Laboratory. Results
available showed that the crack growth rate of the 7. Operating Experience on Modified
modified 9 Cr-1 Mo steel is about the same as that 9 Cr-1 Mo Steel Tubes
observed for 2 1/4 Cr-1 Mo and 12 Cr-1 Mo steel in the
range from room temperature to 538°C (6). Industrial operating experience, which aids
earlier approval of the data package for the ASME
Code, is being obtained by installing tubes of
6.4 Steam and Air Oxidation this alloy in various conventional power plants.
The status of installation of modified 9 Cr-I Mo
The behavior of modified 9 Cr-1 Mo steel and tubes in various utility power plants is summarized
other alloys (2 1/4 Cr-1 Mo, 9 Cr-2 Mo, 12 Cr-1 Mo, in Table V. The range of utilities involved is
and type 304 stainless steel) in superheated steam at international: United States, United Kingdom, and
482 and S38°C are available for a period of 28.33S h. Canada. In nost cases the tubes being replaced are
Results of this study have shown that silicon is very stainless steel. The longest operating time has been
potent in reducing the oxidation rate in steam at reached for tubes Installed at the Kingston Steam
538°C of chromium-molybdenua steels (7). Because of Plant. The tubes installed in the Kingston plant are
its lower silicon content, the modified alloy showed shown in Figure 13. The modified 9 Cr-1 Mo steel
slightly higher weight gain in steam at 538°C than tubes were supplied with type 347 stainless steel
that observed for standard 9 Cr-1 Mo alloy. safe ends. The safe ends were welded on with

Table V. Current status of testing of modified 9 Cr-1 Mo steel tubes in U.S. and foreign steam power plants

Operating Tubes Number

Utility Plant Tube location temperature ^ ^ " of Date Installed Status
p
<°C) tubes

Tennessee Valley Kingston Steam Superheater 593 Type 321 May 1980 Operating
Authority Plant, Unit 5

Aaerlcan Electric Tsnners Creek Secondary 593 Type 304 10 April 1981 Operating
Power Unit 3 superheater

Detroit Edison St. Clair 538 Type 347 February 1981 Operating
Unit 2 Reheater

Central Electric Agecroft Power 590-620 2 1/4 Cr-1 Mo April 1982 Operating
Generating Board Station Superheater
(U.K.)

Ontario Hydro Lambton TCS Reheator 538 Type 304H May 1983 Operating
(Canada) Reheater 538 Std 9 Cr-1 Mo

Ontario Hydro Nantlcoke TGS Secondary 538 2 1/4 Cr-1 Mo 11 1983 Planned
(Canada) superheater
 approval in May 1981. The specification applica-
tion for the forgings, piping, and fittings was
submitted in May 1982. The tube subcommittee M s
approved the specifications, which now must be
approved by the main committee. The plate specifi-
cations are near approval, but the other specifica-
tions are still under consideration by the
appropriate subcommittees.

The data package for the Inclusion of modified

9 Cr-1 Mo steel in Sections I and VIIt of the ASME
Boiler and Pressure Vessel Code was submitted In
June 1982. The action by ASME was started in
October 1982 only after Babcock and Wilcox Company
had requested the approval of seamless modified
9 Cr-1 Mo tubes for Section I construction. \s of
tills writing, the ASME Code case for A213 tubes for
Section I construction was approved through the
Section I committee and was presented as an itea of
new business to the main committee. The action by
the main committee will be announced at the June 1983
meeting. The Section VIII consideration by ASME of
the data package on modified 9 Cr-1 Mo steel is
awaiting a user request.

9.

The status of development and commercialization

of a modified 9 Cr-1 Mo alloy is presented. The alloy
is modified by the additions of niobium (0.06—0.105)
and vanadium (0.18—0.25%). The alloy is recommended
for use in the normalized and tempered condition
(1040°C for 1 h, air cooled to room temperature; 760°C
for 1 h, air cooled to room temperature). Heat treat-
ment, Charpy impact, tensile, and creep properties of
the alloy are discussed in detail and other properties
are described briefly. Some of the key facts about
modified 9 Cr-1 Mo alloy include the following.

1. The ductile-to-brittle transition temperature

(68-J) of modified 9 Cr-1 Mo is lower and the upper-
MODIFIED 9 Cr-1 M o TUBES shelf energy higher than those of standard 9 Cr-1 Mo
alloy. These properties were much better in the
electroslag remelted material.
Figure 13 — The modified 9 Cr-1 Mo steel tubes before
going into operation in the TVA Kingston Steam Power 2. The creep-rupture strength of the modified
Plant. alloy is higher than that of the standard 9 Cr-1 Mo
and 2 1/4 Cr-1 Mo steels for the entire creep tempera-
ture range. The improvement in 105-h creep-rupture
Inconel 82 (ERNiCr3) filler wire. The final welds strength is very significant at temperatures above
between types 347 and 321 (existing tubes) were made 500°C. Higher strength Is also accompanied by total-
on location. elongation and reduction-of-area values higher than 15
and 70Z, respectively.
Tubes in the Agecrofc power station went into
operation in April 1982 and those in Lambton in 3. Higher creep strength of the modified
Hay 1983. Tubes in Kanticoke are expected to go into 9 Cr-1 Mo steel provides design allowable stresses
operation in 1983. This operating experience will be that exceed those of 2 1/4 Cr-1 Mo and standard
very useful for obtaining the approval of this alloy 9 Cr-1 Mo steel for the entire temperature range.
in the ASME Code. At temperatures of at least 500°C, the design
allowable stresses for the modified alloy are twice
those observed for 2 1/4 Cr-1 Mo and standard
8. Status of Commercialization 9 Cr-1 Mo steel.

The use of a aodified or new alloy in actual 4. The specifications for various products of
application requires that It be included in ASTM this alloy have been submitted to ASTM for approval.
specifications and various sections of th'. ASME Boiler A data package has also been submitted to the ASME
and Pressure Vessel Code. The ASTM specifications are Boiler and Pressure Vessel Code for approval of this
in fact prerequisites for the consideration of this material in Sections I and VIII.
alloy by the ASME Code commit:tees. The schedule for
the ASTM and ASME Code approval is as follows: 5. Operating experience on this alloy is being
obtained by installing its tubes in various steam
An application for an ASTM specification for power plants.
the plate and tube product was submitted for
 10. Acknowledgments presented at the Proceedings of the ASM Interna-
tional Conference on Production, Fabrication,
The author thanks the following for their Properties, and Application of Ferritic Steels for
contributions: R. E. McDonald (ORNL) and G. C. Bodine High-Temperature Applications, Warren, Pa.,
(CE, Chattanooga) for contributions to melting, Oct. 6-8, 1981.
fabrication, and heat treatment and helping to prepare
tubes for installation in various power plants; 3. J. Orr, F. R. Beckitt, and G. D. Fawkes, "The
M. J. Stelzman (ORNL) for Charpy V-notch studies; Physical Metallurgy of Chromium-Molybdenum Steels
R. H. Baldwin (ORNL) for tensile and creep testing; for Fast Reactor Boilers," pp. 91—109 in Proceed-
M. C. Cowgill (Westinghouse-Advanced Reactors ings of the International Conference on Ferritic
Division) for creep testing; J. F. King (ORNL) and Steels for Fast Reactor Steam Generators,
C. D. Lundin (University of Tennessee) for welding 30 May—2 June 1977, Volume 1, British Nuclear
studies; R. K. Williams (ORNL) for physical Energy Society, London.
properties; and M. K. Booker (ORNL) for the data
analysis. Our special thanks are also due to the 4. R. K. Williams, R. S. Graves, F. J. Weaver, and
research staff of Climax Molybdenum Company of D. L. McElroy, "The Physical Properties of
Michigan for its contributions to the success of this 9 Cr-1 Mo Steel from 300 to 1000 K," paper
program. Continued encouragement and support of presented at the 17th International Thermal
E. E. Hoffman (DOE, Oak Ridge Operations), Conductivity Conference, Gaithersburg. Md.,
F. Patriarca (ORNL) to Lhe success of this program June 15—19, 1981, In press, Plenum, New York.
also are greatly appreciated. The final manuscript
was prepared by S. G. Frykman. 5. W. B. Jones, "Effects of Mechanical Cycling on
the Substructure of Modified 9 Cr-1 Mo Ferritic
Steel," pp. 221—235 in Ferritic Steels for High-
11. References Temperature Applications, presented at the
Proceedings of the ASM International Conference
1. V. K. Sikka, C. T. Ward, and K. C. Thomas, on Production, Fabrication, Properties, and Appli-
"Modified 9 Cr-1 Mo Steel — An Improved Alloy cation of Ferritic Steels for Kigh-Temperature
for Steam Generator Application," pp. 65—84 in Applications, Warren, Pa., Oct. 6-8, 1981.
Ferritic Steels for High-Temperature Applications,
presented at the Proceedings-of the ASM Interna- 6. L. A. James, Fatigue-Crack Growth Behavior in
tional Conference on Production, Fabrication, Ferritic Alloys for Potential GCFR Structural
Properties and Application of Ferritic Steels for Applications, HEDL-TME 80-71, Hanford Engineering
High-Temperature Applications, Warren, Pa., Development Laboratory, Richland, Wash.,
Oct. 6-6, 1981. Dec. 1980.

2. G. D. Bodine, and R. E. McDonald, "Laboratory 7. J. C. Griess, and W. A. Maxwell, The Long-Term

and Pilot Commercial Process/Product Development Oxidation of Selected Alloys in Superheated Steam
of Modified 9 Cr-1 Mo Ferritic Alloy," pp. 9-20 in at 482 and 538°C, OR.VL-5771, Oak Ridge National
Ferritic Steels for High-Temperature Applications, Laboratory, Oak Ridge, Tenn., July 1981.

DISCLAIMER

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