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45
4 AUTHORS, INCLUDING:
Robert O Ritchie
Judith A. Todd
SEE PROFILE
SEE PROFILE
A new series of 3Cr-Mo-Ni steels has been developed for use in thick section pressure
vessels, specifically for coal conversion (high temperature and high pressure hydrogen)
service. The new steels rely on minor alloy modifications to commercial 2.25Cr-lMo
(ASTM A387 Grade 22 Class 2) steel. Based on evaluations in relatively small heats
(55 kg), the experimental alloys, which employ additions of Cr, Ni, Mo, and V, with Mn
at 0.5 wt pct and C at 0.15 wt pct, display improved properties compared to commercial
steels. Specifically, they show significantly improved hardenability (i.e., fully bainitic
microstructures following normalizing of 400-mm (16-in.) plates), enhanced strength
(i.e., yield strengths exceeding 600 MPa), far superior hydrogen attack resistance and
better Charpy V-notch impact toughness, with comparable tensile ductility, creep rupture
resistance and temper embrittlement resistance. The microstructural features contributing
to these improved mechanical properties are briefly discussed.
INTRODUCTION
The development of second and third generation coal conversion systems, such as proposed large-scale coal liquefaction and gasification processes, has necessitated the
design of large thick-section pressure vessels. L2.3 Materials
requirements for such vessels include weldable steels with
sufficient hardenability to maintain good mechanical properties throughout plate sections up to a maximum of roughly
400 mm (16 in.). In addition, yield strengths in excess of
350 MPa are required with sufficient toughness, creep rupture, fatigue and environmental degredation resistance to
withstand mechanically and environmentally hostile environments, which in certain instances involve hydrogen plus
hydrogen sulfide atmospheres at temperatures of - 5 5 0 ~
and hydrogen gas pressures up to 20 MPa (3000 psi). 3-6
R. O. RITCHIE, E. R. PARKER, and P. N. SPENCER are Professor, Professor Emeritus, and Research Engineer, respectively,
in the Department of Materials Science and Mineral Engineering,
University of California, Berkeley, CA 94720. J.A. TODD is
Assistant Professor, Department of Materials Science, University
of Southern California, Los Angeles, CA 90089. Presented at
American Society for Metals WESTEC '84, March 1984, Los
Angeles, CA.
J. MATERIALSFOR ENERGY SYSTEMS
151
Table I.
Designation
Steel
Steel
Steel
Steel
Steel
152
A
B
C
D
E
EXPERIMENTAL PROCEDURES
The four experimental 3Cr-Mo steels and the reference
2.25Cr-lMo steel were produced as 55 kg (125 lb) laboratory heats by Climax Molybdenum Company using vacuum
induction melting and casting under argon atmospheres.
Chemical compositions in wt pct are listed in Table I. The
ingots were subsequently upset-forged and cross-rolled
to approximately 30 mm thick plates before austenitizing
for 1 hour at 1000 ~ Following austenitization, samples
were either quenched into agitated oil (i.e., cooling rate
1200 ~
or subjected to slow continuous cooling, at
8~
through the transformation range, using a programmable induction furnace. Based on cooling rate data
supplied by Lukens Steel Company, these treatments simulated both the surface and quarter thickness (0.25 T) locations, respectively, of a 400-mm (16-in.) thick plate during
accelerated surface cooling (herein referred to as normalizing). Tempering was carried out in neutral molten salt
baths at temperatures of 650 ~ and principally 700 ~ for
a range of times varying from 1 to 1000 hours. In terms of
the tempering parameter, P, sometimes referred to as the
Larson Miller parameter and defined as T[20+log t]
10-3 where T and t are the tempering temperature (in
Kelvin) and time (in hours), respectively, these treatments
represent a variation in P between 19.0 and 22.4 (or between 34.2 and 40.3 for temperatures in Rankin).
Room temperature uniaxial tensile tests were conducted
on 6.4-mm diameter specimens of 32-mm gauge length,
machined in the longitudinal direction of the plate, according to ASTM Standard E8-69. A displacement rate of
0.5 mm/min was employed. Standard Charpy V-notch
impact specimens were also prepared in the longitudinal
direction, and tested according to ASTM Standard E23-72
over a temperature range from - 1 9 6 ~ to 160 ~ Constant
load creep-rupture tests were performed in air using smooth
round bar longitudinal specimens of initial diameter 6.4 mm
and gauge length 25 ram, according to ASTM Standard
E-139. Tests were carried out at 560 ~ with engineering
stresses between 138 and 345 MPa (20 to 50 ksi).
Susceptibility to temper embrittlement was evaluated by
testing a further series of Charpy impact toughness speci-
Chemical Composition, in wt pct, of Reference 2.25Cr-1Mo and Experimental 3Cr-Mo Steels Tested
C
Mn
Si
Cr
Ni
Mo
AI
0.15
0.15
0.14
0.15
0.14
0.48
0.50
0.49
0.47
0.49
0.21
0.23
0.24
0.22
0.22
2.24
3.00
2.99
3.00
2.95
-0.98
0.98
0.50
0.50
1.01
1.03
1.02
1.50
1.50
--0.21
-0.21
0.006
0.008
0.006
0.006
0.006
0.0034
0.0040
0.0039
0.0036
0.0034
0.014
0.010
0.009
0.008
0.014
RESULTS
Strength and Ductility
The room temperature uniaxial tensile properties of the
four 3Cr-Mo-Ni steels, after slow-cooling (8 ~
and
tempering at 700 ~ for various times between 1 and
1000 hours, are shown in Figure 2. These heat-treatments
represent a range of tempering parameters (temperatures in
Kelvin) between 19.5 and 22.4. It is apparent that all four
Temperin~
1400 -
120(
IOOO*C, I hr
700Oc, 4 h r
~E
)~
I
SI. . . . .
I "~
~8~
F-~
~o'c,
\ /
'~
-%.
,oo
-':
400
~"
"
200 --~ ' " "%7 "Elont.jotion
"-''~
....
ill
"---
O E
~ O [] 0
4L ~ ~ (~
R.A.
UTS
& (ll rl ~
YS
9 9
Elon(J. ~ . . . .
.....
I
I
J
I
o
I0
I00
1000
Tempering Time (hr$) of 7OO"C
Fig. 2 - - R o o m temperature uniaxial tensile properties for experimental
3Cr-Mo-Ni steels, slow-cooled and tempered at 700 ~ as a function of
tempering time and tempering parameter (in Kelvin).
o--f[
0
Toughness
SC 8tT ot 7 0 0 ~
O Steel e
,, Stee, C
4hrs
~.-
200
os,e.,o
o s,ee~E o / / / / ~
]~50 ~,
E
],oo
,5o
-
STEP COOL
ItS
st., 8
\ 495"C, 48 hr
Air cool
'~l176 fst"'c//7--s'"'~
/ 7/-
,5.,
s~*c,, h,
(Y". . . . . .
600
I hr
80
,.,@,,.
al
t/)
Air COOl
700eC, 4 hr
r\
oo~
~0
150-
1000~
~O--~
22
~eOC/min
Parameter
~176 //
-200
-I 0 0
1
0
0
100
200
Test Temperoture (~
Fig. 3 - - C h a r p y V-notch impact toughness transition curves for experimental 3Cr-Mo-Ni steels, slow-cooled and tempered (SC & T) at 700 ~
f o r 4 h.
153
200
>"
td
UNEXPOSED/l
/ P /
~ -.r
0~-][~
-I00
~50
,' , 0 7
,;/,'/'
~o
.,oo,,~o-~..~
f. 9 0Q~'TTOO'C+HE
I
0
TEMPERATURE
I
r00
I
200
(*C)
Steel C ( 3 C r - I M o - I N i - 0 , 2 V )
150
200
150
"' I00
/
Unembrittled
~ T e m p e r Embrittled
~
50
IOO
~ 50--
0 ""-- I
-200
IO
-I00
I OO
Test Temperoture (~
l/
"Temper Embrittled
(Step cooled)
i$0-
! I~t-~1--
-IOO
I00
Test Temperoture (~C:)
-- 150
~ /~Y
50
I
200
Steel E (3Cr-I.SMo-O.SNi-O.ZV)
200
e~
c
LIJ
150
100
ioo
o 50
~Temper Embrittled
(Step cooled)
50
o
O
-2OO
I~"- I
-IOO
I 'r'l I
0
I0o
Test Temperoture (='C)
w
ii
SCS=Tot 7OO~C4hrs S
Unembrittled
- 200
~''"~
-2OO
~ 1oo
200
-'12 1 5 0 -
~J
n.
,'.E'
J /
2
250
/ ///
ZOO
IOC
E
~
SCS=TOt700C 4hr
,~....-,--"T . . . . . . .
STEEL
/ ~//
Steel B ( 3 C t - I M o - I N i )
INi
z ~ / o
0 ~,~r .
-200
ISC
3 Ct-IMo-
I
200
"~t-emper Emlxittled
50--
50
r
-200
-I0O
V"-
IOO
Test Temperoture (*C)
200
Fig. 5--Charpy V-notch impact toughness transition curves for experimental3CR-Mo-Nisteels, slow-cooledand tempered (SC & T) 4 h at 700 ~ in the
temper embrittled (step-cooled) and unembrittledconditions.
154
Table II.
Unembrittled
A
B
C
D
E
- 13
-105
- 25
- 20
- 10
*Slow cooled
,o1, (8 ~
Temper Embrittled
~
~
~
~
~
--40
-I0
25
15
Shift
Unembrittled
Temper Embrittled
(J)
122
206
186
203
176
(J)
-165
175
175
163
~
~
~
~
AT
-65 ~
15 ~
45 ~
25 ~
tempered
~ered 4,. hr at 700 ~
Tempering
1501 I
Parameter
,,~
1400[-
~o
~,,
~,~
HYDIRoGE__
N EXPOSED
II
- 200
H ~ ' T - T R E A T E D S'EELS
80
I\
I ~
--'"
I %'"
,~oo~/~...
150
o . . ._. . . , a . . . _ _ o . _ . L
~_
. . .... . ... . . .
....
'=
~...d'n~..~
I00
I ' , \
L><2
's
5O
".
..
'x "
"
"II-.
"~"-L~."-.
~oo
Yield Strength /
-'<
,=t
O~
:~
- -:>-~-::--.
,_"
:0
~._~.-e--~
.~/~,...~......~.~"t
20C
CB
:o
OE
"&Elongation
=
I
Tempering
A 000
R.A.
~ ~ $ UTS
IOC
//f
Z
I,u
U
<I
O.
I
!
I
I
~E
o.
5C
rr
"I"
t.3
. . . . . . . . .
7/-
,-,~
150
I
~
,,/0
/ . . . .
/1
-E
~
I
- IOO~
o
STEEL B
50
D STEEL O
O STEELE
(HEAT-TREATED)
0 ~.(I
0
_J
AND
HEAT TREATE'D
I
I
//
/
/
~N-EXPOSED
7,
tlJ
t
0
0----
I0//
200
"I//
l-
)-
I000
,,
Oh
IO
I00
Time (hrs) at 7 0 0 " C
S?EL B (HEAT-TREATED)7
._1
& (! I! ~, YS
.....
9 9 9 9 Elong.-- . . . .
o~'f
t5o
I0
I00
TEMPERINGTIME(HRS)AT 700=C
(b)
I000
155
,501
Condition
Slow-cooled, 4 hr at 650 ~
Slow-cooled, 4 hr at 700 ~
Oil Quenched, 4 hr at 650 ~
Oil Quenched, 4 hr at 700 ~
U.T.S.
(MPa)
ZOO
~J~ IOC
Unembrittled\
~
o.
,~
~--Temper Embrittled
/~
o
J=
u
{600eC/IOOOh/17MPo)
-200
'~
C/~HydrogenExposed
~11
-I00
150
0
I O0
Test Temperature (*C)
50
0
200
Yield Stress
(MPa)
S,~e___L~._(3Cr-'
N~______)
Mo-1
~
pet Elong.*
pct Redn.
Area
Upper Shelf
Charpy Energy
(J)
UE
HE
UE
HE
UE
HE
UE
HE
UE
HE
691
627
660
545
552
552
537
502
781
779
782
664
647
661
638
616
20
24
24
24
22
23
22
25
75
73
76
76
73
73
73
71
189
206
190
230
162
161
186
178
Steel B
40 ft-lb (54 J)
Transition Temp.
(~
UE
-100
-105
-115
-120
HE
~
~
~
~
-23
-40
-50
-23
~
~
~
~
156
17 MPa)
I00
-- -- 0
*~ 8 O
. . . . .
C~
(]5
13
09
00
6O
SC a T o t 7 0 0 ~
9 Steel A
0 Steel B
Steel C
I~ Steel D
0 Steel E
"o
0.I
(Bose 2 . 2 5 C r - I M o )
(3Cr-IMo-INi)
( 3 C r - I Mo-I Ni-O.?V)
(3Cr-I 5 Mo-OSNi)
( 3 C r -I.5 MO-0.5 Ni-O.2V)
I
I
1
I
I0
I00
Rupture Time (hours)
I
I000
I0,000
Fig. 101Creep rupture ductility (pct RA) v s time to rupture for experimental 3Cr-Mo-Ni steels, slow-cooled and tempered4 h at 700 ~ from
constant load tests at 560 ~ at stresses between 138 and 345 MPa.
comparable with those of 2.25Cr-lMo steel. Furthermore,
at longer lives (above 1000 hours), the 3Cr-Mo-Ni steels
actually out perform commercial 2.25Cr-lMo alloys, particularly in the V-containing C and E steels which tend to
display the best performance at the lower applied stresses.
Hardenability
For cooling rates as slow as 8 ~
typical of the conditions at quarter thickness of a 400-mm thick plate during
normalizing, commercial 2.25Cr-lMo steel generally has
inadequate hardenability to ensure fully bainitic microstructures, as evidenced by the substantial proportion
( - 4 0 pct) of the polygonal ferrite in as-cooled structures
[Figure ll(a)]. The experimental 3Cr-Mo-Ni steels, conversely, with their increased Cr + Ni additions, show
vastly enhanced hardenability and 100 pct granular bainitic
structures after a similar slow cooling rate of 8 ~
[Figure 1l(b)].
Microstructures
As noted above, the microstructure of all four 3Cr-Mo-Ni
steels was found to be 100 pct granular bainite, with a prior
austenite grain size of approximately 50/xm (Figure 12). In
the as-cooled untempered conditions, fine autotempered
J. MATERIALSFOR ENERGY SYSTEMS
M3C (cementite) precipitates (Figure 13) and films of retained austenite (Figure 14) are evident between bainitic
laths. X-ray and magnetic saturation studies on Steel B have
indicated that the proportion of such interlath austenite is
approximately 17 pct in the as-cooled condition, compared
to 5.5 to 7 pct in the as-quenched state. 29
On tempering at 700 ~ for 1 hour, fine accicular intralath carbides (--0.05 /xm in size) together with coarser lath
boundary carbides (--0.25 /zm in size) were observed and
identified, using selected area diffraction, as cubic M23C6
(Figure 15). 32No evidence of the hexagonal M2C or M7C3 or
orthorhombic M3C carbides could be detected. This is in
stark contrast to 2.25Cr-lMo steel where, at 700 ~ M3C
precipitation can persist up to tempering times of 30 hours
(Figure 16).33 After 1000 hours at 700 ~ M23C6 precipitates in the 3Cr-Mo-Ni steels are typically 0.5 to 1 bcm in
size (Figure 17) with additional evidence of the Mo-rich
M6C precipitates (Figure 18), and in the C and E steels VC
VOL. 6, NO. 3, DECEMBER 1984
157
Fig. 13
T r a n s m i s s i o n e l e c t r o n m i c r o g r a p h s of s l o w - c o o l e d
3Cr-1Mo-INi Steel B in the untempered condition, showing (a) bright field
of ferrite (a) and_f'me autotempered cementite (0), (b) dark field of cementite from (210)o reflection of (c) selected area diffraction (SAD)
pattern, and (d) interpretation of (c). 32
DISCUSSION
On the basis of the TEM and STEM studies (Figures 15, 17,
and 18), it is clear that the increased Cr and Ni content in the
present 3Cr-Mo-Ni series of steels leads to a markedly accelerated tempering response compared to 2.25Cr-lMo
steel. In particular, the iron and chromium-rich M23C6 carbide replaces the less stable M2C, M3C and M7C3 carbides
J. MATERIALS FOR ENERGY SYSTEMS
Fig. 1 7 - - T r a n s m i s s i o n e l e c t r o n m i c r o g r a p h s o f s l o w - c o o l e d
3Cr-lMo-lNi Steel B after tempering at 700 ~ for 1000 h, showing
(a) bright field of ferrite and M23C6 precipitates, (b) SAD pattern, and
(c) interpretation of (b). 32
Fig. 1 8 - - T r a n s m i s s i o n e l e c t r o n m i c r o g r a p h o f s l o w - c o o l e d
3Cr-I.5Mo-0.5Ni-0.2V Steel E after tempering at 700 ~ for 1000 h,
showing (a) bright field of ferrite, and M23C6 and M6C carbides, (b) dark
field of (026) M6C reflection of (c) SAD pattern, and (d) interpretation
of (c).32
Pct Cr
Pct Mo
Pct Fe
Pct V
/
~j
'
'
200
ot 650 =C/4 h
lo Unexposed
. . . .
I /% H:~exposed , *
i O0 -
Type
Carbide
(6000c,
o, o
--2:
150
~--
~.~--'e'-
I00
Steel B
Fine ppts (0.1 /zm)
Elongated ppts (1.0/zm)
Massive ppts (1.0/xm)
43.9
24.7
37.7
11.6
32.7
11.2
44.5
42.6
51.1
Steel D
Fine ppts
Elongated ppts
Massive ppts
17.2
36.3
46.0
36.5
17.5
7.3
Steel E
Fine ppts
Elongated ppts
Massive ppts
8.8
t0.6
I 1.9
4.0
45.8
43.1
--
M23C6
--
M6C
:~
--
M23C6
~.
46.3
46.2
46.7
---
M6C
M23C6
--
M;~3C6
1.2
43.6
45.0
86.0
---
/
.s"
VC
M6C
M6C
-200
/~
/
~
-IO0
-,)
225Cr-IMo Steel
Z~I~"
at 6500C/4h
- 50
9
f H2 e~posed(550 C. 14 MPa)
0
I00
200
Temperoture (=C)
Fig. 1 9 - - C o m p a r i s o n o f Charpy V - n o t c h impact t o u g h n e s s o f
2.25Cr-lMo steel and experimental 3Cr-lMo-lNi Steel B, both quenched
and tempered 4 h at 650 ~ prior to, and after, 1000 h high temperature
exposure to gaseous hydrogen (550 to 600 ~ 14 to 17 MPa pressure).
159
vanadium containing Steels C and E may be preferred because of their superior creep strength.
Finally, the present series of steels compare very favorably with other recently developed 3Cr-Mo alloys for thick
section, hydrogen service pressure vessel application,
namely the 3Cr-I.5Mo-0.1V steels developed by Climax
Molybdenum~9'2~'23 and the 3Cr-lMo-0.25V, Ti, B steels
developed by the Japan Steel Works. 24 As shown in Figures
20 to 22, all three series of steels out perform 2.25Cr-lMo
steels. However, whilst the creep rupture (Figure 20) and
temper embrittlement resistance of the three 3Cr-Mo steels
is similar, the current 3Cr-Mo-Ni alloys appear to offer the
best combinations of strength and toughness (Figures 21
and 22).
Code
A
B
C
D
E
Yield
Stress
UTS
Elong.**
RA
MPa (ksi)
MPa (ksi)
Pct
Pct
641
779
772
799
821
24
24
26
22
21
73
73
75
73
74
Alloy
2.25Cr-lMo
3Cr-lMo-lNi
3Cr-IMo-INi-0.2V
3Cr-l.5Mo-0.5Ni
3Cr-I.5Mo-0.5Ni-0.2V
496
627
593
655
676
(72)
(91)
(86)
(95)
(98)
(93)
(113)
(112)
(116)
(119)
Upper
Shelf
Charpy
Energy
J (ft-lb)
122
206
186
203
176
(90)
(152)
(137)
(150)
(130)
40 ft-lb
Transition
~ C (~
- 13
-105
- 25
- 20
- 10
(
9)
(-157)
( - 13)
(4)
(
14)
Creep
Rupture Life
at 200 MPa
(560 ~
hr
457
269
947
212
1253
160
CONCLUSIONS
A new series of 3Cr-Mo-Ni steels has been developed to
provide alternatives to 2.25Cr-1Mo steel for thick section
pressure vessel applications involving high temperatures (up
to 550 ~ and high hydrogen pressures (up to 18 MPa). The
nominal compositions of these steels are 3Cr-1Mo-1Ni and
3Cr-l.5Mo-0.5Ni, with and without 0.2V. Based on evaluations on 55 kg heats the new steels are found to be superior
to 2.25Cr-lMo steel with respect to hardenability, room
temperature strength, impact toughness and resistance to
hydrogen attack, and to be similar with respect to room and
elevated temperature ductility, creep strength and rupture
ductility and temper embrittlement resistance. In addition,
their mechanical properties compare very favorably to the
recently developed 3Cr-1.5Mo-0.1V Climax Molybdenum
and 3Cr-lMo-0.25V, Ti, B Japan Steel Works steels, and
actually are somewhat superior to these steels with respect
to strength and toughness.
ACKNOWLEDGMENTS
This work was supported by the Department of Energy,
Advanced Research and Development Fossil Energy Materials Program, through the Oak Ridge National Laboratory
(ORNL), under Subcontract 7843 with the University of
California, Berkeley, under Union Carbide Contract W7605-eng-26 with the U.S. Department of Energy. The authors would like to thank R.W. Swindeman of ORNL for
many helpful discussions, Dr. D. S. Sarma for transmission
electron microscopy assistance, and T. George, R.K. Anders, R. I. Huntley, and L. -H. Chan for experimental help.
REFERENCES
161
162
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Amer. Soc. Mech. Eng., New York, NY, 1984.
26. T. Wada and W.C. Hagel: Metall. Trans. A, 1976, vol. 7A,
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27. Jin Yu and C.J. McMahon: Metall. Trans. A, 1980, vol. IIA,
pp. 277-300.
28. S. Sato, S. Matsui, T. Enami, and T. Tobe: in Application of
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(ASTM A387D)," National Research Institute for Metals, Japan,
1974.
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pp. 257-268.
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