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INTER-_.[ I 170. 2 h
MEDIATE 9--
FINE --4-! bOff4h
6 9 0 ~ 12h
i,i LOW "--e, t6, 3.10h
IE INTER--..,.
3 MEDIATE- 593ji h
I-- HIGH - - - I .
~_~_~8 15h
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i. --~96,48 h
O.
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LIJ
I-- I ~ F U R N A C E
~ C O O L
~ 315
WQ WQ
TIMI i-
(a)
21/'~ Cr STEEL W ITPI VARYING AMOUNT OF Mo
~
AIR COOL Fig, l - H e a t treatments used to
produce temper e mbri ttlem en t
m: (a) 21A Cr-I Mo steels doped
2~'4 C r - 0 . 5 Mo ii wath P or Sn, (b) 2 88 Cr steels
with varying Mo content.
AIR
COOL
21/4 C r - I I Mo ii 690, 6 h
2 [/4 C r - 1.3 Mo ii 690, 6 h
(b)
800 -
700
M6C -50 9 9
-75
-
- TEMPERINGTREATMENTS
9 . 65o-c Oh
/ Ip 6 9 0 " C 12h i
600 - ~ ~'-,~,.+ CrTC 3 ~ --100 I 2 3 //
t--
- Fe3C + M~ I I I I //
500
| ~ j.~
- 26o Rc
400
Fe3C + E C A R B I D E
9"r 9149
I I I I I I I, I I 180 I ~// I
I 2 3 7
1.0 5 I0 50 I00 500 I000 5000 I0000
AGEING TIME AT 5 2 0 " C (10 "~h)
TEMPERING TIME (h)
Fig. 3-Variation with aging time of the 4 ft-lb (5.4 J) transition tem-
Fig. 2-Data of Baker and Nutting 22 showing the sequence of carbide perature and the hardness of the fine-grained 0.04 P steel, aged at
formation during tempering of a quenched 288Cr-1 Mo steel. Symbols 520~ showing different embrittlement kinetics at three hardness
H, I, and L indicate high, intermediate and low hardness tempering levels.
treatments used in present study.
*ANI. Cr - 0.4 C steel doped with 0.02 pct P showeda A0 of 150 ~ after 20 h High (H) M2C f o r m a t i o n about to c o m -
at 520~ 24 mence
e i a l C r - M o steels25'z6t- (which c o n ta in Mn and Si). I n t e r m e d i a t e (I) M2C f o r m a t i o n a l m o s t c o m -
?For commercialCr-Mosteels,40 valuesover 100~ are not uncommon.25"26 plete
Low (L) M2C about to be r e p l a c e d by
H o w e v e r , the low s u s c e p t i b i l i t y of the p r e s e n t s t e e l M~C3 and M23C6
to e m b r i t t l e m e n t is c o n s i s t e n t with p r e v i o u s r e p o r t s
about the b e n e f i c i a l r o l e of Mo, 1-4 the n a t u r e of which
T h e r e f o r e , one would e x p e c t that the aging t r e a t m e n t
r e m a i n s to be made c l e a r .
at 520~ would have r e l a t i v e l y l i t t l e e f f e c t on the Mo
It is a p p a r e n t that the k i n e t i c s of e m b r i t t l e m e n t a r e
c o n c e n t r a t i o n in the f e r r i t e in the L and I c o n d i t i o n s ,
not the s a m e f o r the d i f f e r e n t h a r d n e s s l e v e l s . In the
but that M2C f o r m a t i o n at 520~ in the H condition
s a m p l e s with low o r i n t e r m e d i a t e h a r d n e s s the e m -
b r i t t l e m e n t is rapid, and a s t e a d y s t a t e is r e a c h e d would p r o d u c e s i g n i f i c a n t c h a n g e s in the a m o u n t of
within ~ 100 h; t h i s type of b e h a v i o r is to be e x p e c t e d Mo a v a i l a b l e to s c a v e n g e P .
if the s e g r e g a t i o n is c o n t r o l l e d by the d i f f u s i o n r a t e In o r d e r to i n v e s t i g a t e this f u r t h e r , X - r a y a n a l y s e s ,
of the P . H o w e v e r , f u l l - s c a l e e m b r i t t l e m e n t t a k e s of e x t r a c t e d c a r b i d e s and c h e m i c a l a n a l y s e s of the
liquid e x t r a c t ( r e p r e s e n t i n g the m a t r i x ) w e r e c a r r i e d
m u c h l o n g e r in the high h a r d n e s s condition; w e l l o v e r
out. F i g u r e 4 g i v e s a c o m p a r i s o n of the r a t e s of i n-
1000 h is r e q u i r e d to r e a c h a s t e a d y s t a t e . T h u s , the
c r e a s e of i n t e r g r a n u l a r f r a c t u r e at ~ - 1 0 0 ~ (an a l -
C r - M o s t e e l d i f f e r s f r o m the N i - C r s t e e l not only in
t e r n a t i v e m e a s u r e of the r a t e of e m b r i t t l e m e n t ) with
the o v e r a l l e m b r i t t l e m e n t s u s c e p t i b i l i t y , but a l s o in
the t y p e s of c a r b i d e found at v a r i o u s s t a g e s of the
the k I n e t i c s of e m b r i t t l e m e n t in s o m e conditions of
aging p r o c e s s . A s a n t i c i p a t e d , the slow e m b r i t t l e m e n t
heat t r e a t m e n t . (See a l s o F i g . 4(a).)
in the H s a m p l e s was a c c o m p a n i e d by the slow p r e -
Th e b e h a v i o r in the h i g h - h a r d n e s s condition is c o n -
c i p i t a t i o n of M2C. F o r I and L s a m p l e s m o s t of the
s i s t e n t with that o b s e r v e d e a r l i e r in a N i C r M o s t e e l
M2C had a l r e a d y p r e c i p i t a t e d d u r i n g the t e m p e r i n g
doped with P w h e r e slow e m b r i t t l e m e n t at 500~ co r n -
_b?_ 20
+ F i g . 3). However, d u r i n g the prolonged aging t r e a t -
ment, the c o n c e n t r a t i o n of d i s s o l v e d Mo d e c r e a s e d
s t e a d i l y as the M2C c a r b i d e p r e c i p i t a t e d , t h e r e b y
o
p e r m i t t i n g m o r e e m b r i t t l e m e n t . Tile s i m u l t a n e o u s
~)tz
cku- 0 drop in the d i s s o l v e d Cr content in the H s t e e l i n d i -
c a t e s the p a r t i t i o n i n g of Cr to M2C. F o r the I and L
0.6 i i
LLO~ (b) s a m p l e s in the a s - t e m p e r e d condition, the c o n c e n t r a -
t i o n s of d i s s o l v e d Mo were a l r e a d y low due to the
~ 04 M2C and M7C3 p r e c i p i t a t i o n . T h e r e f o r e , with l e s s
,.---" MzC + FesC
l---r
<DO ~ Mo a s s o c i a t e d with P, m o r e P s e g r e g a t i o n could o c c u r .
H e r e , the d e c r e a s e of d i s s o l v e d alloy content d u r i n g
the aging t r e a t m e n t was v e r y s m a l l c o m p a r e d to that
~-Ld
in the H s p e c i m e n s . However, this s m a l l d e c r e a s e
tgN 0 J I I // I
I 2 3 7 s e e m s to have allowed enough P s e g r e g a t i o n to offset
the softening effect (see F i g . 3).
AGEING TIME A T 5 2 0 * C ( l O S h )
T h e s e r e s u l t s support the idea that the e m b r i t t l e -
Fig. 4-Correlation between the rate of increase of: (a) intergranular
fracture at ~- 100~ and (b) M2C precipitation in the 0.04 P steel, at ment k i n e t i c s depend on the a m o u n t of d i s s o l v e d Mo,
three hardness levels. which can change due to c a r b i d e p r e c i p i t a t i o n . How-
e v e r , it should be noted that the c o n c e n t r a t i o n of d i s -
t r e a t m e n t , and the f r a c t i o n of M2C i n c r e a s e d only solved Cr d e c r e a s e s d u r i n g the aging t r e a t m e n t in a
slightly, if at all, d u r i n g aging. T h i s was c o n f i r m e d m a n n e r s i m i l a r to that of Mo. Since Cr is known to
by the e x t r a c t i o n r e p l i c a s in which the H s a m p l e s e x - e n h a n c e P s e g r e g a t i o n , z4,29,s~ a d e c r e a s e in the d i s -
hibited none of the n e e d l e - s h a p e d M2C p a r t i c l e s b e - solved Cr content ( p a r t i c u l a r l y at the high h a r d n e s s
fore aging, but an i n c r e a s i n g amount of t h e m d u r i n g level) is expected to be b e n e f i c i a l , in c o n t r a s t with
the aging t r e a t m e n t . In the I and L s a m p l e s , the the o b s e r v e d b e h a v i o r . T h e r e f o r e , the effect of the
t y p e s and m o r p h o l o g i e s of c a r b i d e r e m a i n e d m o r e or d e c r e a s i n g Cr m u s t be o v e r p o w e r e d by that of the d e -
l e s s c o n s t a n t d u r i n g aging. It should be noted that the c r e a s i n g Mo. A n o t h e r point is that, despite the p r e s -
lattice p a r a m e t e r of the MzC was found to be c o n s i d - ence of m o r e Mo to s c a v e n g e P, the I s a m p l e s show
e r a b l y s m a l l e r than that of Mo2C, i n d i c a t i n g that C r at l e a s t as much i n t e r g r a n u l a r f r a c t u r e a s the L s a m -
had p a r t i t i o n e d into the M2C carbide.27'28 p l e s . T h i s may be a s c r i b e d to the effect of h a r d n e s s ,
The r e s u l t s of c h e m i c a l a n a l y s i s of the m a t r i x e x - per se.
t r a c t , given in Fig. 5, show that, as expected, the H
s a m p l e s had the l a r g e s t a m o u n t of dissolved* Mo and 9 HIGH HARDNESS
*Meaningin the fernte phase, ratherthanin carbides. 9 INTERMEDIATE HARDNESS
P 9 LOW HARDNESS
Cr in the a s - t e m p e r e d condition. The fact that only
FeTo3 Ir ] "
0 F i " i i I/ i
o 08T_~
I (o)
[0 f~"""~ONE FACET
m 06 ~ /H I o /
> [/CLEAVAGE
J
o 04 oI t [ i 41 I
0.2 ~ 2 ~ " \L
I--
0/
CI
M~ I (b) f J
I I I 2 I 0
26 I r , 2 r I
I (b) i~~ , . . ~ CLEAVAGE
H w
(~ 2.2 9 0I I i //
/I
LtJ
>
j
o
o~
(/)
1.8
I ~ .
9
Cr529 I (C)
Fez~ I~ - -
I I
i =i--
I " - - - - - - CLEAVAGE
I
o I I I , II i
f 2 3 7
l.O I I ~ # J AGEING TIME AT 520 *C (lOSh)
I 2 3 7
Fig. 6-Averaged Auger peak height ratios from fracture surfaces of the
AGEING TIME AT 5 2 0 ~ (lOSh) 0.04 P steel aged at 520~ and fractured at ~-100~ (a) Px20/FeT03,
Fig. 5-Variation of: (a) Mo and (b) Cr in solution with aging time for (b) Mo186/FeTo3,(c) Crs29/Fe?o3.Error bars represent range of values
the 0.04 P steel at three hardness levels. measured.
I
LOW HARDNESS LOW HARDNESS
'" -25
O - 0
I--
ne-
uJ
W
-50 o'.--...._ -40 -40
I--
n- 0 o
bJ
0_
300
I , , i
HARDNESS
,
250
I L ,
(DPH)
, J [
200
, , J =E
-40 -4o -..<
Fig. 7-Effect of hardness on 5.4 J transition temperature of the fine- V- -eO -8o
grained 0.04 P steel at various aging times.
Z
I = I = I L I
T h e i n t e r g r a n u l a r f a c e t s on s p e c i m e n s f r a c t u r e d at I- 3 5 7 9 3 5 7 9
~ - 1 0 0 ~ in UHV w e r e a n a l y z e d in the SAM. T h e r e -
suit s w e r e e x p r e s s e d as a p e a k - h e i g h t - r a t i o (PHR) =5 I t , '~,.i ' i ~lG~ '
using the F e 703 eV peak as the r e f e r e n c e , and a r e HIGH HARDNESS
~x\, HARDNESS
shown in F i g . 6. Th e v a r i a t i o n of the a v e r a g e i n t e r - -
g r a n u l a r P c o n c e n t r a t i o n a p p e a r s to be s i m i l a r to
that of the p e r c e n t a g e of i n t e r g r a n u l a r f r a c t u r e . Th e
-4( -
-40
i n c r e a s e of the P12o PHR is c o n s i s t e n t with the slow
e m b r i t t l e m e n t k i n e t i c s f o r the H s a m p l e s and the
r a p i d k i n e t i c s in the I and L s a m p l e s . T h u s , t h e s e -8( -80
r e s u l t s show that in the H condition both the p e r c e n t -
I , 1 , I , I I , I ~ I , I
age of e m b r i t t l e d b o u n d a r i e s and the P c o n c e n t r a t i o n 3 5 7 9 .3 5 7 9
on t h e s e b o u n d a r i e s i n c r e a s e d s l o w l y with aging at
PRIOR AUSTENITIC GRAIN SIZE (ASTM No )
520~ Th e Mo~s6, Cr529, and C273 P H R s w e r e much
Fig. 8-Influence of austenitic grain size on the 5.4 J transition tem-
l a r g e r on g r a i n b o u n d a r i e s than on c l e a v a g e f a c e t s , perature of the 0.02 and 0.04 P steels at three hardness levels.
p r e s u m a b l y due m a i n l y to i n t e r g r a n u l a r a l l o y e a r -
b i d e s , but a l s o to s e g r e g a t e d a l l o y e l e m e n t s . h i g h e r m a t r i x h a r d n e s s . Both t h e s e t e n d e n c i e s a r e
Th e t r a n s i t i o n t e m p e r a t u r e s f r o m F i g . 3 a r e plotted q u a l i t a t i v e l y c o n s i s t e n t with the e m b r i t t l e m e n t e q u a -
vs the m a t r i x h a r d n e s s in F i g . 7. It can be s e e n that tion of T a k a y a m a e l a l . 3z It should be noted that the
the i s o c h r o n a l c u r v e s have a v a r i e t y of s l o p e s b e c a u s e slow e m b r i t t l e m e n t o b s e r v e d in the high h a r d n e s s
of the slow k i n e t i c s at the high h a r d n e s s l e v e l . F o r s a m p l e s o c c u r s in a l l g r a i n s i z e s .
e x a m p l e , the 100 h c u r v e shows a d i s t i n c t c o n c a v e -
d o w n w a r d n e s s , which is c o n t r a r y to the b e h a v i o r of E f f e c t of V a r i a t i o n in Mo Content of the S t e e l
P doped N i - C r s t e e l s . 24 T h e l a t t e r d a t a w e r e plotted
at constant l e v e l s of i n t e r g r a n u l a r s e g r e g a t i o n , r a t h e r Since the w o r k by P o w e r s , s'6 it has b e e n known that
than c o n s t a n t aging t i m e s ; the p r e s e n t i s o e h r o n a l Mo ad d i t i o n s of m o r e than 0 3 wt pct do m o r e h a r m
c u r v e s at s h o r t aging t i m e s do not r e p r e s e n t i s o a d - than good. Th e r e s u l t s of Charpy t e s t s by Wada and
s o r p t i o n co n d i t i o n s , as is c l e a r f r o m F i g . 6. T h e H a g e l 7 on a s e r i e s of 2.25 Cr s t e e l s a r e shown in
c u r v e s tend to s t r a i g h t e n out at l o n g e r aging t i m e s , F i g . 9. E a c h s t e e l had to be t e m p e r e d d i f f e r e n t l y to
because isoadsorption conditions are ultimately provide a constant as-tempered tensile strength, be-
reached. c a u s e of the v a r y i n g Mo content. 7 T h e i r r e s u l t s c l e a r l y
S i m i l a r e x p e r i m e n t s w e r e done on the 0.02 P s t e e l , show a m i n i m u m in F A T T a r o u n d 0.5 to 0.7 pct Mo.
which was found to exhibit v i r t u a l l y the s a m e g e n e r a l Th e d a t a in F i g . 10 show that the m a t r i x h a r d n e s s is
e m b r i t t l e m e n t c h a r a c t e r i s t i c s a s the 0.04 P s t e e l , a l - e s s e n t i a l l y c o n s t a n t above 0.6 pct Mo. T h e r e f o r e , it
though the t r a n s i t i o n t e m p e r a t u r e s w e r e a l w a y s l o w e r is a p p a r e n t that the high Mo e f f e c t is not due to h a r d -
than t h o s e of the 0.04 P s t e e l , a s would be e x p e c t e d . ness changes.*
T h e v a r i a t i o n of t r a n s i t i o n t e m p e r a t u r e with p r i o r *Notethat the maximumhardness differencebetween 0.5 and 1.3 pct Mom
a u s t e n i t e g r a i n s i z e was e x a m i n e d f o r the 0.04 P and Fig. 10 ]s 17 DPHunits. From the data m Fig. 7 this wouldproduce at most a
0.02 P s t e e l s , a s shown in F i g . 8. T h e g r a i n s i z e e f - 10 ~ increasem transition temperature, as opposed to the 70 ~ differenceindi-
f e c t i s m o r e p r o n o u n c e d in the 0.04 P s t e e l , which is cated m Fig. 9.
c o n s i s t e n t with the r e s u l t s of Capus. 3~ A l s o , t h e r e is Th e r e s u l t s of X - r a y a n a l y s e s of c a r b i d e p a r t i c l e s
a t e n d e n c y for the g r a i n s i z e e f f e c t to be g r e a t e r at extracted electrolytically from their specimens are
z
o
I.--
or"
L.I-
M7 C3
I'--
b_ _
40 - / -
t ~ e
LtJ /-
r ~__ o o ~ ~ n,- __ @/@ m
I l 1 ~ 0 I i 0 I i <I
~,)
M2 C
0 02 04 0.6 08 I0 12 14
TOTAL Mo CONTENT (wt %) o I I I I I I
0,4 0,8 1,2
Fig. 9-Fracture appearance transitmn temperatures (FATT) of 2 88 Cr
steels with varying total Mo content in both the quenched-and-tem- TOTAL Mo CONTENT(wt%)
pered and step-cooled conditions. 7 Fig. l l-Types of carbide present m the step-cooled 288Cr steels with
varying total Mo content.
g i v e n in F i g . 11. It can be s e e n that the i n c r e a s e d
e m b r i t t l e m e n t at > 0.7 pct Mo is a c c o m p a n i e d by M2C d i s s o l v e d C r c o n c e n t r a t i o n i n c r e a s e s a s M7C3 is r e -
p r e c i p i t a t i o n ! T h i s is the r e s u l t of the l o n g e r t e m p e r - placed by M2C (Fig. 11). The p r e s e n c e of the m i n i m u m
ing t i m e s applied to the high Mo s t e e l s which showed in the d i s s o l v e d Cr content c o r r e s p o n d s to the m i n i -
a high r e s i s t a n c e to softening; the p r o l o n g e d t e m p e r - m u m in the t r a n s i t i o n t e m p e r a t u r e .
ing allowed M~C p r e c i p i t a t i o n to o c c u r . F i g u r e 11 Our i n t e r p r e t a t i o n of the Wada and Hagel r e s u l t s
shows that the f r a c t i o n of M2C i n c r e a s e d as the total a r e , t h e r e f o r e , as follows: A s the Mo content is r a i s e d
Mo content i n c r e a s e d . At the s a m e t i m e , the f r a c t i o n
of M7C3 d e c r e a s e d , due to the fixed C content. Since , i i i 9 o U OF PENN '
MTCs is a Cr r i c h c a r b i d e , the d e c r e a s e of MTCa would x OUTSIDE LAB
r e s u l t in m o r e Cr in solution, t h e r e b y p e r m i t t i n g
08
more Cr-P cosegregation.
The r e s u l t s of the a n a l y s e s of the e x t r a c t f r o m the
f e r r i t e m a t r i x for Mo a r e p r e s e n t e d in F i g . 12. T h r e e
s e p a r a t e a n a l y s e s a r e shown; two out of the t h r e e i n -
0
06 S --f:-
Ld
dicate that the c o n c e n t r a t i o n of d i s s o l v e d Mo i n c r e a s e s >~ o4
s t e a d i l y to a s a t u r a t i o n l e v e l at a total Mo content of 0
/.o//"
~ 0.7 pct. As the Mo content is i n c r e a s e d beyond 0.7
pct, it a l l goes to f o r m m o r e c a r b i d e . F o r the two
c u r v e s which show s a t u r a t i o n beyond 0.7 pct Mo, the
l e v e l of one c u r v e c o r r e s p o n d s to 75 pct of the other,
i m p l y i n g that the e r r o r between t h e m is s y s t e m a t i c .
0 02 04 06 0.8 I0 12 14
A s i m p l e c a l c u l a t i o n shows that the higher l e v e l of
Mo is m o r e p l a u s i b l e . * E v e n the t h i r d a n a l y s i s shows TOTAL Mo CONTENT (wt%)
* F o r the 1.3 Mo steel, the calculated values of the dissolved Cr and Mo are
Fig. 12-Concentration of Mo in the ferrite phase for the step-cooled
1.67 and 0.75 pct respectively. 2% Cr steels with varying total Mo content.
I I r I
a m a r k e d change in slope at ~ 0.7 pet total Mo and is
thus r o u g h l y c o n s i s t e n t with the other two. The r e s u l t s
of the a n a l y s e s of the Cr c o n c e n t r a t i o n in solution in 2.0
the f e r r i t e a r e given in Fig. 13. It is c l e a r that the
O~ / x~
o 1 6 ~ Cr/ x~ x
I I I I I I I
260 ^~x I
0
-- I00
"r- ,3 ~.2
13,. 240 -- 98 123
LLI Mo
03 -- 96 m > 0.8
U.I _J
i..iJ Z
220
z
(:3
n,"
-- 94
a
a:
I
o~~ 0.4 ~"~ ......
-r" - 92
200
l I 1 I I I 0 i i t i
0.2 0 4 0.6 0 8 1.0 1.2 14 0 04 08 12 I6
TOTAL Mo CONTENT (wt % ) TOTAL Mo CONTENT (wt %)
Fig. 10-Hardness of the step-cooled 2 88Cr steels with varying total Fig. 13-Concentrations of Mo and Cr in the ferrite phase for the step
Mo content. cooled 288Cr steels with varying total Mo content,
AGI Iz.I
X B exp "RT -r 15-
x, : [11 <
1 + j =n-~ XB (exp R-T-AG~ 1) W
r, I0-
j=l
I
ir
0b,-
w h e r e B r e f e r s to the bulk s o l i d s o l u t i o n which c o n -
tains components. Since C d o e s not e n t e r d i r e c t l y I.L
into the i n t e r g r a n u l a r s e g r e g a t i o n in the p r e s e n t c a s e , 0
(xJ
we can t r e a t P doped CrMo s t e e l a s a f o u r component m- I I I I I 1
s y s t e m . Using the r e g u l a r solution m o d e l we can a p - 0.2 0 4 0.6 0.8 1.0
p r o x i m a t e the i m p o r t a n t AG i t e r m s a s follows:38*
DISSOLVED Mo(wt%)
*These come from a straightforward extension of Guttmann's ternary regular
Fig. 1 6 - I n t e r g r a n u l a r c o n c e n t r a t i o n of P at 5 2 0 ~ {.in t e r m s o f the
solution model to a quaternary solution; the detailed derivation3~ can be supplied
Pl2o PHR) as a f u n c h o n of the Mo c o n c e n t r a t i o n in solution for the
upon request to the authors.
0.04 P steel at several hardness levels.
o
50 O p
<[
rr
I : m
9 9
oom
9
9
Y
<[
20 0-
;#-<...." at 520~ (a) of P and Mo and
(b) of P and Cr.
&O& 9 9
W
n
o0~ 9 9
0
9
b_
I0- 0
0
0
o4 AA
n
,,j,
%
I I I I I l I I I I
0 2 4 6 8 0 2 4 6 8 I0 12
Mo186/FeTo 3 PH R (%) Cr529/Fe705 PHR (%)
(a) (b)
and P. The positive ~ ' t e r m s would produce c o s e g r e - et al 4~ and has r e c e n t l y been d e m o n s t r a t e d conclusively
gation of Mo + P and Cr + P; hence, the t h r e e (X/~ by the f r e e - s u r f a c e s e g r e g a t i o n study of G r a h a m and
--X B) would a l l i n c r e a s e and there would be mutual Yen. 41 More r e c e n t work by DiDio and G r a h a m 42 has
e n h ~ c e m e n t of s e g r e g a t i o n of P by Mo and Cr. T h e r e - d e m o n s t r a t e d the P scavenging effect of Mo by use of
fore, unless X~ were somehow d e c r e a s e d , an i n c r e a s e the s a m e technique.
in bulk concentration of Cr or Mo would be expected to If it is a s s u m e d that the Mo + P scavenging effect
produce enhanced P s e g r e g a t i o n . is the r e s u l t of the formation of Mo3P and that Mo3P
The p r e s e n t r e s u l t s indicate that i n c r e a s e s in Cr do and Fe3P can f o r m a continuous, isomorphous solid
enhance P s e g r e g a t i o n , but that i n c r e a s e s in Mo con- solution, then Guttmann's 43 adaptation of H i l l e r t ' s 44
tent r e t a r d it. The l a t t e r can be seen in F i g . 16 where r e g u l a r solution a n a l y s i s of c a r b i d e s o l u b i l i t i e s can
data from s e v e r a l conditions of t h e r m a l h i s t o r y a r e be used to e s t i m a t e the X~ v a l u e s at v a r i o u s l e v e l s of
c o l l e c t e d and it is shown that the s e g r e g a t e d P l e v e l X ~ o . The e x p r e s s i o n for X~ f r o m such an a n a l y s i s is
d e c r e a s e s as the Mo concentration in the f e r r i t e in- given by :
c r e a s e s . This can only happen if Mo acts as a s c a v e n -
exp(4.97 - 4490/T) [5]
g e r of P and l o w e r s the mobile P concentration so
X~
much that the ,large LxGp is m o r e than offset by the 1 + [exp 5 5 3 6 / T - - 1]Xffr 3
reduction in X ~ . The c l a s s i c example of this b e h a v i o r
in s t e e l s is, of c o u r s e , the Mn + S r e a c t i o n . B
Since the Mo does not scavenge all of the P, one If we take the m e a s u r e d v a l u e s of XMo for the v a r i o u s
would expect to see some c o s e g r e g a t i o n of Mo and Cr a s - t e m p e r e d conditions and calculate X~, we can plot
with the r e m a i n i n g P. This is supported by Fig. 17 these on c a l c u l a t e d c u r v e s of X~ and XB at v a r i o u s
IYlO
which shows that both the Cr and Mo Anger peak t e m p e r a t u r e s (usingEq. [5]) as shown ifi F i g . 19. It
heights i n c r e a s e with the P peak height. Since n e i t h e r can be seen that this calculation is consistent with
Cr nor Mo a r e surface active in Fe to any a p p r e c i a b l e the e x p e r i m e n t a l r e s u l t s ; X~ in the H condition
extent, this behavior indicates c o s e g r e g a t i o n . It is not is r e d u c e d significantly below the bulk concen-
p o s s i b l e to say how much Mo and Cr have c o s e g r e - t r a t i o n in the alloy. (This a n a l y s i s gives only a p p r o x i -
gated, b e c a u s e p a r t of the signal f r o m the i n t e r g r a n u - mations because of the v a r i o u s s i m p l i f i c a t i o n s made.)
l a r f a c e t s came f r o m g r a i n boundary c a r b i d e s . The a s - t e m p e r e d values of X~ obtained above can
The i n t e r p r e t a t i o n of the effects of Cr and Mo is be i n s e r t e d into Eq. [1] and e s t i m a t e s of the other
aided by the m e t a l l o g r a p h i c r e s u l t s of Kaneko et a139 p a r a m e t e r s can be made to calculate X~ for the e a r l y
on the effects of v a r i o u s alloy e l e m e n t s on the solu- stage of segregation at 520~ When this was done, ~8
b i l i t y of P in F e , r e p r o d u c e d in F i g . 18. They have the range of X~ v a l u e s for the t h r e e h a r d n e s s condi-
shown that Mo i n t e r a c t s much more strongly with P tions was found to be 0.54 to 0.57, which is obviously
in Fe than does Cr. T h e i r r e s u l t s a r e consistent with too s m a l l to explain the d i f f e r e n c e s found here in the
the p r e c i p i t a t i o n of some kind of Mo phosphide. It e m b r i t t l e m e n t behavior
~k (see F i g . 4(a)). In addition,
should be noted that Nb, Ti, and Zr should be even a calculation of X ~ vs t e m p e r a t u r e indicated that the
more potent P s c a v e n g e r s than Mo. The scavenging steep t e m p e r a t u r e dependence of X~p would occur above
of P by Ti was indicated by e a r l i e r work of Ohtani 800~ However, in the p r e s e n t r e s u l t s this o c c u r s b e -
Alloying
Element (wt %)
(b) z iO-i L
n
Fig. 18-Results of Kaneko e t al, 39 showingeffects of various alloying
elements on the solubility of P in e-Fe: (a) as a functmn of tempera-
ture for 1 pct alloying addition and (b) at 1000~
0-2
tween 400 and 600~ which, of c o u r s e , a l l s t u d i e s of _n I - c-
t e m p e r e m b r i t t l e m e n t show. It a p p e a r s that t h e r e is
d
n e e d for b e t t e r t h e r m o d y n a m i c data for the r e l e v a n t o
s o l u t e s in F e b a s e d a l l o y s b e f o r e we can b e g i n to be
q u a n t i t a t i v e in c a l c u l a t i o n s of e q u i l i b r i u m s e g r e g a t i o n a io -3
W
l e v e l s . F u r t h e r m o r e , the p r e s e n t a n a l y s i s a s s u m e s <~ 520-C
that F e , P, and Mo a r e s u b s t i t u t i o n a l ; that is, that .-I
they c o m p e t e for a fixed n u m b e r of g r a i n b o u n d a r y s
_1
s i t e s . T h i s m a y not be the e a s e , and a m o r e e l a b o r a t e < I I I L
model may be called for .45 0 0.25 0.5 0.75 1.0 25
W h e n e v e r one finds e o s e g r e g a t i o n of a m e t a l l o i d DISSOLVED M o ( w t % )
and a m e t a n i e alloy e l e m e n t in a s t e e l t h e r e is the
Fig. 19-Calculated solid solubdity of P m a Fe-Mo-P alloy at the
p o s s i b i l i t y that the e m b r i t t l i n g potency of the m e t a l - tempering and aging temperatures used for the P steel, as a function
loid e l e m e n t will be a l t e r e d . A d r a m a t i c e x a m p l e of of the No concentration in the ferrite.
~0~0/
/ 0 " - ' - ' 0 -
0
SUMMARY
It has been shown that t e m p e r e m b r i t t l e m e n t of
CrMo s t e e l s by P can be influenced significantly by
0 O..."~'G 0 O ~
the concentrations of Mo and Cr in solution in the f e r -
j r i t e phase and that these concentrations change as a
t~ 0.5 r e s u l t of the f o r m a t i o n of v a r i o u s c a r b i d e s and thus
u.J
they depend on the t h e r m a l h i s t o r y of this s t e e l . Tin
o~
at concentrations up to 0.04 pet was found not to e m -
I I b r i t t l e an otherwise pure 2.25 C r - 1 Mo s t e e l . It was
0.6 1.2 a l s o shown that, although scavenging of P continues
to i n c r e a s e at concentrations of dissolved Mo of at
TOTAL Mo CONTENT ( w t % ) l e a s t 1 pet, i n c r e a s e s in total Mo content above 0.7
Fig. 20-Transition temperature, P~2o/FeT03 PHR, transition tempera-
ture shift per umt intergranular P concentratmn, and Mo concentratmn pet a r e actually l e s s d e s i r a b l e under n o r m a l conditions
m ferrite as a function of the total Mo content for 2 88 Cr steels. of heat t r e a t m e n t , b e c a u s e at higher total Mo contents