I he ttects of Composition and Carbide

Precipitation on Temper Embrittlement of 2.25

Cr-1 Mo Steel Part I. Effects of P and Sn
JIN YU AND C. J . McMAHON, J r .

T e m p e r e m b r i t t l e m e n t of 2.25 C r - 1 Mo s t e e l d o p e d with P and Sn was s t u d i e d s y s t e m a t i c -

a l l y . C a r b i d e e x t r a c t i o n by e l e c t r o l y s i s , X - r a y d i f f r a c t i o n , t r a n s m i s s i o n ( r e p l i c a ) e l e c -
t r o n m i c r o s c o p y , c h e m i c a l a n a l y s i s of the m a t r i x , and scanning A u g e r m i c r o p r o b e a n a l y -
s i s w e r e conducted to d e t e r m i n e the effect of c a r b i d e p r e c i p i t a t i o n and s u b s e q u e n t v a r i a -
tion of the Mo c o n c e n t r a t i o n in s o l u t i o n on the s e g r e g a t i o n of P . T h e s e a n a l y s e s w e r e
c o r r e l a t e d with the d u c t i l e - t o - b r i t t l e t r a n s i t i o n t e m p e r a t u r e ( m e a s u r e d by u s e of a s l o w -
bend t e s t ) , a s w e l l a s h a r d n e s s m e a s u r e m e n t s and f r a c t o g r a p h i c i n f o r m a t i o n obtained by
s c a n n i n g e l e c t r o n m i c r o s c o p y . The r e s u l t s i n d i c a t e that the p r i n c i p a l r o l e of Mo i s to
s u p p r e s s e m b r i t t l e m e n t by s c a v e n g i n g of P, p r e s u m a b l y by a M o - P compound f o r m a t i o n ,
t h e r e b y d i m i n i s h i n g P s e g r e g a t i o n . H o w e v e r , due to the s t r o n g e r i n t e r a c t i o n b e t w e e n
Mo and C, Mo is p r e c i p i t a t e d in an MaC c a r b i d e d u r i n g t e m p e r i n g o r aging, and the m a -
t r i x is d e p l e t e d of Mo. The P t h e r e b y r e l e a s e d s e g r e g a t e s at a r a t e c o n s i s t e n t with the
r a t e of M2C p r e c i p i t a t i o n . A t a Mo c o n c e n t r a t i o n > 0.7 p c t the b e n e f i c i a l effect of Mo is
d e c r e a s e d due to enhanced M2C p r e c i p i t a t i o n , the content of Mo in s o l u t i o n r e m a i n i n g
e s s e n t i a l l y c o n s t a n t . The M2C i s f o r m e d at the e x p e n s e of C r - r i c h MvC3; t h i s r e s u l t s in
m o r e C r in solution, t h e r e b y p e r m i t t i n g m o r e C r - P c o s e g r e g a t i o n , and e m b r i t t l e m e n t
i n c r e a s e s . T i n was found not to p r o d u c e t e m p e r e m b r i t t l e m e n t in t h i s s t e e l when p r e s e n t
at c o n c e n t r a t i o n s up to 0.04 p c t .

RESEARCHinto the p r o b l e m of t e m p e r e m b r i t t l e - with the e f f e c t s of Mn and Si in conjunction with P .

merit of a l l o y s t e e l s f r o m a p h e n o m e n o l o g i c a l point of
view has o v e r a p e r i o d of many d e c a d e s involved e x -
p e r i m e n t s on both c o m m e r c i a l s t e e l s and s p e c i a l l y
doped l a b o r a t o r y s t e e l s of c a r e f u l l y c o n t r o l l e d c o m -
p o s i t i o n . M o s t of o u r p r e s e n t u n d e r s t a n d i n g has c o m e
f r o m the l a b o r a t o r y s t e e l s in which one f a c t o r at a
t i m e could be v a r i e d . A s t h e s e s t u d i e s have p r o g r e s s e d
the b e h a v i o r of the m o r e c o m p l i c a t e d c o m m e r c i a l
s t e e l s has b e c o m e m o r e and m o r e u n d e r s t a n d a b l e .
Up to the p r e s e n t t i m e m o s t of the l a b o r a t o r y s t u d -
i e s have e m p l o y e d s t e e l s containing Ni, u s u a l l y s i m -
p l e N i - C r s t e e l s , s i n c e t h e s e u s u a l l y exhibit the g r e a t -
e s t s u s c e p t i b i l i t y to t e m p e r e m b r i t t l e m e n t . H o w e v e r ,
o v e r the p a s t d e c a d e the r e a l i z a t i o n that C r - M o s t e e l s
can a l s o be highly s u s c e p t i b l e has s p r e a d . T h e now
f a m o u s H i n c k l e y Point t u r b i n e d i s c f a i l u r e in 1969
did much to s e t the s t a g e f o r the c u r r e n t i n t e r e s t in
these steels.
One of the m o s t w i d e l y used C r - M o s t e e l s for t h i c k -
w a l l e d s t r u c t u r a l a p p l i c a t i o n s has the b a s e c o m p o s i -
t i o n 2.25 C r - 1 Mo, and c o m m e r c i a l h e a t s g e n e r a l l y
contain Mn and Si (added i n t e n t i o n a l l y ) a s w e l l a s r e -
s i d u a l l e v e l s of P and Sn which a r e p o t e n t i a l e m b r i t -
t l i n g e l e m e n t s . The p r e s e n t t w o - p a r t r e p o r t g i v e s the
r e s u l t s of what i s a p p a r e n t l y the only c o m p r e h e n s i v e
study for p u b l i c a t i o n of l a b o r a t o r y s t e e l s in which the
2.25 C r - 1 Mo c o m p o s i t i o n was u s e d a s a b a s e and the
above e l e m e n t s w e r e a d d e d i n d i v i d u a l l y . The p r e s e n t
p a p e r d e a l s with the e f f e c t s of P and Sn and P a r t II
JIN YU is Post-doctoral Fellow, Max-Planck-Institut Fi~r Eisen-
forschung, 4 Di]sseldorf, West Germany. C. J. McMAHON, Jr. is
Professor of Materials Science and Engineering, Department of Materials
Science and Engineering, University of Pennsylvama, Philadelphia, PA
19104.
Manuscript submitted June 29, 1979.
ISSN 0360-2133180/0211-0277500.75/0
METALLURGICAL TRANSACTIONS A 9 1980 AMERICAN SOCIETY FOR METALS AND
THE METALLURGICALSOCIETY OF AIME
It i s w i d e l y r e c o g n i z e d that the a d d i t i o n of Mo in
s t e e l i n h i b i t s t e m p e r e m b r i t t l e m e n t . 1-3 H o w e v e r , the
m e c h a n i s m by which t h i s o c c u r s i s not y e t c l e a r .
R e c e n t w o r k 4 on a N i - C r - M o s t e e l doped with 0.06 P
showed that e m b r i t t l e m e n t was i n i t i a l l y s u p p r e s s e d ,
but that it l a t e r o c c u r r e d s l o w l y with p r o l o n g e d aging
in a m a n n e r s u g g e s t i v e of c a r b i d e p r e c i p i t a t i o n k i -
n e t i c s . T h e r e f o r e , it was s u g g e s t e d that the p r i n c i p a l
r o l e of Mo is to tie up P, but that the e v e n t u a l p r e -
c i p i t a t i o n of Mo in c a r b i d e s would allow P s e g r e g a t i o n
in p r o l o n g e d e x p o s u r e to e l e v a t e d t e m p e r a t u r e s .
One p u z z l i n g a s p e c t of the Mo effect, a p p a r e n t l y
f i r s t r e p o r t e d by P o w e r s , 5'6 is the e x i s t e n c e of an
o p t i m u m a m o u n t of Mo. A d d i t i o n s of Mo b e y o n d 0.7
p c t have been found to enhance e m b r i t t l e m e n t r a t h e r
than r e d u c e i t . 7 P r e v i o u s c o n j e c t u r e s about t h i s p h e -
n o m e n o n have involved a p o s s i b l e effect of Mo on the
d i f f u s i v i t y of p8,9 o r on the h a r d n e s s of the t e m p e r e d
s t e e l , m One m a i n p u r p o s e of t h i s w o r k w a s to d i s c o v e r
the u n d e r l y i n g m e c h a n i s m by which Mo i n h i b i t s P i n -
d u c e d e m b r i t t l e m e n t and the o r i g i n of the high Mo
effect.
EXPERIMENTAL PROCEDURE
High purity Fe-2.25 Cr-I Mo-0.2 C steels to which
were added P and Sn, individually, the compositions of
which are listed in Table I, were vacuum-induction
meRed from high purity Cr, Mo, and C and electro-
lyric Fe, and the ingots were hot forged and swaged
and then machined into specimen blanks. These were
heat treated in capsules of Vycor (below I000 ~ or
quartz (above I000 ~ C) according to the diagram in
Fig. l(a). The three austenitizing temperatures pro-
vided coarse, intermediate, and fine grains (ASTM
VOLUMEl lA, FEBRUARY 1980-277
G r a i n s i z e 3 to 3.5, b to 5.b, and t to 8, r e s p e c t i v e l y ) . A s e r i e s of 2.2b Ur s t e e l s having d i f f e r e n t a m o u n t s
T h e t e m p e r i n g t r e a t m e n t s g a v e high, i n t e r m e d i a t e , of Mo, p r e v i o u s l y s t u d i e d by Wuda and H a g e l , 7 w e r e
and low h a r d n e s s l e v e l s (R c 30, 20, and 13, r e s p e c - received as broken Charpy bars. The compositions
tively). l i s t e d in T a b l e I show that e a c h heat had e s s e n t i a l l y
s i m i l a r l e v e l s of r e s i d u a l e l e m e n t s and of Mn and Si.
T h e heat t r e a t m e n t s ( p e r f o r m e d a t C l i m a x M o l y b -
Table I. Chemical Compositions, Wt Pct d e n u m Co.) involved the following (see F i g . l(b) and
R e f . 7):
Des~.gnat~on C~" Mo C P Sn Mn Si S A1 1. A u s t e n i t ~ z a t i o n f o r 1 h at 9 5 5 ~ C, which g a v e an
a u s t e n i t i c g r a i n s i z e of ASTM No. 8.5 to 9.
0.02P 2.24 1.0" 0.2* 0,017 0.001
0.04 P 2.58 1.0" 0.2* 0,036 0.001 2. A d i f f e r e n t t e m p e r i n g t r e a t m e n t for e a c h heat
0.02Sn 2.26 1.0" 0.2* 0,002 0.024 (because of the d i f f e r e n c e s in Mo content) to p r o v i d e
0.04Sn 2.23 1.0" 0.2* 0.002 0.043 an a s - t e m p e r e d t e n s i l e s t r e n g t h of 100 k s i .
288 2.21 0.00 0.13 0,024 0.006 0.45 0.23 0,016 0.022 3. Step cooling to p r o v i d e an i d e n t i c a l condition of
288 2.21 0.48 0.13 0,024 0.45 0.23 0.016 0,024
e m b r i t t l e m e n t in a l l h e a t s .
288 2.2 1 0.71 0.13 0,024 0.45 0.23 0,016 0,025
288 2.21 0.92 0.13 0.024 0.45 0.23 0.016 0.028 T h e t e s t s p e c i m e n s w e r e 6.35 m m in d i a m , and c o n -
2]/4Cr-l.lMo 2.21 1,12 0.13 0.024 0.45 0.23 0,016 0.028 t a i n e d a 6 0 deg c i r c u m f e r e n t i a l n o t c h with a r o o t r a -
2 88 2.21 1.31 0.13 0.025 0.46 0.23 0.016 0.029 d i u m of 0.13 ram, 11 m m f r o m the end. The d i a m b e -
*Nominal composition. n e a t h the notch was 4.33 r a m . T h e 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 m e a s u r e d by a s l o w - b e n d t e s t . n E a c h

AUSTENITIZE TEMPER AGE OR S T E P COOL

IGRAIN SIZE HARDNESS

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
Q: I
i. --~96,48 h
O.
=E
I 4~8,72 h
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

AUSTENITIZE TEMPER I TEMPER 2 AGE

955, i h
2 1/4 Cr -- 0 MO
593, I h
"--~.4o, is h
~5,24h
L~95,48 h
AIR WATER
7z.
~,~U iRsNACECOOL
COOL QUENCH

~
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

2~/4 Cr--O 7 Mo tt 690, 4 h

2~4 Cr-0.9 Mo tl 690, 5 h

21/4 C r - I I Mo ii 690, 6 h
2 [/4 C r - 1.3 Mo ii 690, 6 h
(b)

2 7 8 - V O L U M E 11A, FEBRUARY 1980 METALLURGICAL TRANSACTIONS A

s p e c i m e n was loaded to f r a c t u r e as a c a n t i l e v e r b e a m
in a s p e c i a l l y d e s i g n e d jig attached to an I n s t r o n t e s t -
ing m a c h i n e at a d i s p l a c e m e n t r a t e of 0.085 mm//s
and at a t e m p e r a t u r e between - 1 9 6 and 200~
Liquid n i t r o g e n was s p r a y e d on the s p e c i m e n s for
the t e s t t e m p e r a t u r e s b e t w e e n - 196 and 0~C, and
s i l i c o n e oil was used a s a heating m e d i u m for the
t e s t s done b e t w e e n 0 and 200~ An i r o n - c o n s t a n t i n
t h e r m o c o u p l e was spot-welded to the s p e c i m e n j u s t
b e s i d e the notch in o r d e r to p r o v i d e t e m p e r a t u r e c o n -
t r o l of I~ The f r a c t u r e e n e r g y was m e a s u r e d by
i n t e g r a t i n g the a r e a u n d e r the l o a d - d e f l e c t i o n c u r v e ,
and the r e s u l t s were e x p r e s s e d as a 5.4 J (4 ft-lb)
t r a n s i t i o n t e m p e r a t u r e ; this was found to give the b e s t
d e f i n i t i o n of the t r a n s i t i o n t e m p e r a t u r e .
M e t a l l o g r a p h i c s a m p l e s were etched with s a t u r a t e d
aqueous p i c r i c acid with 1 g of s o d i u m t r i d e c y l b e n z e n e
sulfonate added p e r 100 m l of solution as a wetting
agent. 12 The g r a i n s i z e s were m e a s u r e d by the l i n e a r
i n t e r c e p t method, and the m e a s u r e d a v e r a g e g r a i n
d i a m e t e r was c o r r e c t e d by a g e o m e t r i c a l factor of
1.65 to a p p r o x i m a t e the r e a l g r a i n s a s t e t r a k a i d e c a -
hedra.13
To identify the f r a c t u r e mode, s c a n n i n g e l e c t r o n
m i c r o g r a p h s at 300 m a g n i f i c a t i o n were taken at the
top and bottom notch root a r e a s , where f r a c t u r e
s t a r t e d and ended, and in the c e n t r a l a r e a , and i n t e r -
g r a n u l a r f a c e t s were outlined on a s e m i t r a n s p a r e n t
p a p e r . By cutting the p a p e r and m e a s u r i n g the weight
f r a c t i o n of i n t e r g r a n u l a r a r e a s , the i n t e r g r a n u l a r p e r -
centage was d e t e r m i n e d . The a v e r a g e value of those
t h r e e a r e a s was used to r e p r e s e n t the f r a c t u r e mode.
In o r d e r to s e p a r a t e the c a r b i d e s f r o m the f e r r i t i c
m a t r i x without c a r b i d e d i s s o l u t i o n , e l e c t r o l y s i s at
c o n s t a n t c u r r e n t d e n s i t y 14-16 was c a r r i e d out with an
e l e c t r o l y t e of 15 pct s o d i u m c i t r a t e - 1 pct p o t a s s i u m
t h i o c y a n a t e (KCNS) s o l u t i o n Y -19 About 0.6 g of the
s a m p l e ( p r e v i o u s l y polished with no. 600 g r i t e m e r y
p a p e r ) was d i s s o l v e d in 300 mt of the e l e c t r o l y t e u n -
d e r a c u r r e n t d e n s i t y of 5 to 10 m A / c m 2 at 1 to 1.5 V
for 24 to 30 h. is The s a m p l e was s u s p e n d e d in a P t
b a s k e t having n u m e r o u s holes to allow e a s y flow of
the e l e c t r o l y t e ; a Pt wire s e r v e d a s a cathode.
D u r i n g the e l e c t r o l y s i s , the pH of the e l e c t r o l y t e
tended to r i s e , and u n d e s i r a b l e compounds such as
f e r r o u s or f e r r i c c i t r a t e c o m p l e x e s of unknown c o m -
position or Fe4(Fe(CN)6)3 could f o r m . Hence, the pH
of the solution was c o n s t a n t l y checked by a pH m e t e r
and was c o n t r o l l e d at 7 + 0.2 by dropwise additions of
HC1. The e l e c t r o l y t e was c o n s t a n t l y s t i r r e d with a
p l a s t i c coated magnet in o r d e r to p r e v e n t any pH
g r a d i e n t or Fe r i c h zone n e a r the s p e c i m e n s u r f a c e .
A f t e r the e l e c t r o l y s i s , p r e c i p i t a t e s a d h e r i n g to the
s u r f a c e of the s a m p l e were r e m o v e d by flushing with
d i s t i l l e d w a t e r , and the m e t a l l i c deposit on the cathode
was d i s s o l v e d with c o n c e n t r a t e d HC1 and t r a n s f e r r e d
b a c k into the e l e c t r o l y t e . The c a r b i d e p a r t i c l e s were
s e p a r a t e d f r o m the e l e c t r o l y t e by a c e n t r i f u g e at
75,000 g r a v i t y . The c l e a n e l e c t r o l y t e solution was
pipetted and the c a r b i d e s were collected together,
washed with d i s t i l l e d H20 many t i m e s u n t i l the c a r -
b i d e s were c o m p l e t e l y free of any o r g a n i c s u b s t a n c e
f r o m the e l e c t r o l y t e , and then the c a r b i d e s w e r e d r i e d .
The e x t r a c t e d c a r b i d e s were identified by X - r a y dif-
f r a c t i o n using a D e b y e - S e h e r r e r c a m e r a (D = 114.6
ram) with a V f i l t e r ; Cr K s r a d i a t i o n at 40 kV and a
METALLURGICALTRANSACTIONSA
tube c u r r e n t of 20 mA was used with e x p o s u r e t i m e s
of 12 to 18 h. The 20 v a l u e s of the l i n e s on the dif-
f r a c t i o n p a t t e r n s were m e a s u r e d , and i n t e n s i t i e s
were m e a s u r e d by a m i c r o d e n s i t o m e t e r . The d e t a i l s
of the method used for q u a n t i t a t i v e a n a l y s i s of d i f f r a c -
tion p a t t e r n s f r o m m i x t u r e s of m o r e than two c a r b i d e
types a r e g i v e n in Ref. 38 and can be supplied by the
a u t h o r s upon r e q u e s t .
C a r b i d e i d e n t i f i c a t i o n was a l s o done by 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 s c o p y . C a r b o n v a p o r was d e p o s i t e d on
the etched s u r f a c e and the thin f i l m was s t r i p p e d in
2 pct Nital. The e x t r a c t i o n r e p l i c a was e x a m i n e d with
a P h i l l i p s 300 e l e c t r o n m i c r o s c o p e .
The s e p a r a t e d e l e c t r o l y t e solution was once again
f i l t e r e d by W a t t m a n n u m b e r 42 p a p e r and c h e m i c a l l y
a n a l y z e d to give the Mo, Cr, and F e c o n c e n t r a t i o n s in
the s o l u t i o n . The r a t i o of M o : F e and C r : F e was c a l -
culated to give the wt pct of Mo and Cr r e m a i n i n g in
the f e r r i t e . The m o l y b d e n u m thiocyanate s p e c t r o -
p h o t o m e t r i c method 2~ was used for the Mo a n a l y s i s ,
and the a t o m i c a b s o r p t i o n method was used for the
Cr a n a l y s i s . The d i c h r o m a t e t i t r a t i o n method was
used for the F e a n a l y s i s . 2~
A s c a n n i n g A u g e r m i c r o p r o b e (SAM) was used for
the study of g r a i n b o u n d a r y s e g r e g a t i o n . S p e c i m e n s
were f r a c t u r e d in situ, u n d e r a v a c u u m of < 1 10-1~
T o r r at a t e m p e r a t u r e of ~ - 1 0 0 ~ U s u a l l y about
twenty s p e c t r a were r e c o r d e d f r o m d i f f e r e n t g r a i n
b o u n d a r i e s , along with a n o t h e r five s p e c t r a f r o m
c l e a v a g e f a c e t s . A n i s o t r o p y in the g r a i n b o u n d a r y
s e g r e g a t i o n was studied by use of a m u l t i p l e x s y s t e m ,
and for this over 100 g r a i n b o u n d a r y facets were
a n a l y z e d in each s p e c i m e n . The o p e r a t i n g conditions
for the A n g e r a n a l y s e s were as follows:
Incident beam energy 5 KeV
Incident b e a m size 2O
Primary beam current 20 to 30 ~A
Modulation voltage 6 eV
E l e c t r o n m u l t i p l i e r voltage 1 keV
Time constant 0.1 s
Sensitivity 20 (or 100
When i n f o r m a t i o n on the s u r f a c e c o m p o s i t i o n p r o -
file was needed, ion s p u t t e r i n g was p e r f o r m e d with
p u r i f i e d A r + gas u n d e r the following c o n d i t i o n s :
Ar pressure 5 10-5 T o r r
Voltage d i f f e r e n c e b e t w e e n
the anode and the t a r g e t 5 keV
Filament current 5 mA
RESULTS
A s i d e f r o m the i n t e n t i o n of studying the effect of
h a r d n e s s per se, the t h r e e t e m p e r i n g t r e a t m e n t s were
chosen so that they p r o d u c e d d i s t i n c t l y d i f f e r e n t s t a g e s
of c a r b i d e f o r m a t i o n , thus t h r e e d i f f e r e n t l e v e l s of Mo
in s o l u t i o n in the f e r r i t e p h a s e . T h e s e t h r e e c o n d i -
t i o n s a r e i n d i c a t e d in F i g . 2 which g i v e s the r e s u l t s
of B a k e r and Nutting 22 on the k i n e t i c s of c a r b i d e f o r -
m a t i o n in a 2.25 C r - 1 Mo s t e e l . Although t h e i r s t e e l
contained Mn and Si, which have some effect on c a r -
bide f o r m a t i o n , as will be shown s e p a r a t e l y , 23 t h e i r
r e s u l t s can be used as a p p r o x i m a t e g u i d e l i n e s in the
present report.
VOLUME llA, FEBRUARY 1980 279
 DATA ON C A R B I D E FORMATION I 1 0 0 4 ~.P // ' |
(FROM BAKER & NUTTING) O
o 0 FINE G.S

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.

m e n c e d a f t e r s e v e r a l hundred h and continued beyond

E m b r i t t l e m e n t by P h o s p h o r u s
T h e v a r i a t i o n of the t r a n s i t i o n t e m p e r a t u r e with
aging t i m e at 520~ f o r the 0.04 P s t e e l with the fine
g r a i n s i z e and s e v e r a l h a r d n e s s / c a r b i d e c o n d i ti o n s,
is g i v e n in F i g . 3. (Note that the t i m e s c a l e is in
t h o u s a n d s of h o u r s . ) It can be s e e n that the t e m p e r
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 of this s t e e l is not l a r g e
in any c a s e ; the t r a n s i t i o n t e m p e r a t u r e shift (A0)
h a r d l y e x c e e d s 40~ e v e n in the m o s t e m b r i t t l e d c o n -
di t i o n . T h i s i s in c o n t r a s t with the much l a r g e r e m -
b r i t t l e m e n t by P in N i - C r s t e e l s . 24,29. o r in c o m m e r -
103 h. It was p o s t u l a t e d that t h i s b e h a v i o r was due to
the slow r e l e a s e of P f r o m the Mo s c a v e n g e d sta t e a s
Mo was r e m o v e d f r o m f e r r i t e by c a r b i d e f o r m a t i o n . *
*We do not know whetherMo and P form an actual compound m these steels
or somekind of clusterm the fernte phase; for conveniencewe refer to the Mo
not in carbides as beingin the fernte.
It can be s e e n f r o m F i g . 2 that the t h r e e conditions
of the p r e s e n t C r M o s t e e l can be c h a r a c t e r i z e d as
follow s:
H a r d n e s s Condition Stage of C a r b i d e F o r m a t i o n

*ANI. Cr - 0.4 C steel doped with 0.02 pct P showeda A0 of 150 ~ after 20 h
at 520~ 24
e i a l C r - M o steels25'z6t- (which c o n ta in Mn and Si).
?For commercialCr-Mosteels,40 valuesover 100~ are not uncommon.25"26
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
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
r e m a i n s to be made c l e a r .
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
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
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
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
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
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
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
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 - 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
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 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
heat t r e a t m e n t . (See a l s o F i g . 4(a).)
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 -
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
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 -
High (H) M2C f o r m a t i o n about to c o m -
mence
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 -
plete
Low (L) M2C about to be r e p l a c e d by
M~C3 and M23C6
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
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
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 ,
but that M2C f o r m a t i o n at 520~ in the H condition
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
Mo a v a i l a b l e to s c a v e n g e P .
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 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
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-
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 -
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 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
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
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 -
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
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

280-VOLUME l lA, FEBRUARY 1980 METALLURGICAL TRANSACTIONS A

 9 HIGH HARDNESS 0.8 pet Mo was p r e s e n t in s o l u t i o n in the H s t e e l when
9 INTERMEDIATE HARDNESS a l l the c a r b i d e was MsC is p r e s u m a b l y due to the p a r -
(27 9 LOW HARDNESS
.~ (30 ~ I t i t i o n i n g of Mo to the MaC. T h i s l e v e l of d i s s o l v e d
(a) Mo is a p p a r e n t l y enough to s u p p r e s s most of the e m -
Z
b r i t t l e m e n t in the f i r s t few h u n d r e d h of aging (see
(.9

_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.

METALLURGICAL TRANSACTIONS A VOLUME IIA, FEBRUARY 1980 281

 H I L Oh
IOOh
[
l ' ' ' ' I ' ' ' I ' ' IO00h
A 3000h
U
o
I I
0.02
i
P
I i I I
x
i
STEP COOL 0 0 4
] 1
P

I
LOW HARDNESS LOW HARDNESS
'" -25
O - 0
I--
ne-
uJ
W
-50 o'.--...._ -40 -40
I--

z -75 -80 -80

o
I--
k L I i I , I , l , I q l
z -I00 3 5 7 3 5 7 9
I.--
W
oc I I I I
~ -125 D INTERMEDIATE HARDNESS

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

2 8 2 - V O L U M E I1A, FEBRUARY 1980 METALLURGICALTRANSACTIONS A

 I I I I I p
I o UNEMBRITTL~'D I I I I I/~ I I
8 0 , e-, 9 STEP-COOLED
| j ~

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,

METALLURGICAL TRANSACTIONS A VOLUME l l A , FEBRUARY 1980-283

 I i i I i i i i s i s t e n t with the above r e a s o n i n g , a s shown in F i g . 14.
The Plzo PHR shows a m i n i m u m v a l u e when the t o t a l
Mo content is a r o u n d 0.5 to 0.7 p c t . The o n e - t o - o n e
,,12 c o r r e s p o n d e n c e b e t w e e n the Cr~29 and Plz0 P H R s i s
(a)
c o n s i s t e n t with the c o s e g r e g a t i o n p h e n o m e n o n . T h e
MO186 PHR is found to i n c r e a s e m o n o t o n i c a l l y , r e -
f l e c t i n g the i n c r e a s e d bulk c o n c e n t r a t i o n ; the Mo p e a k
o
is p r e s u m a b l y due to Mo c a r b i d e s , d i s s o l v e d Mo, and
s e g r e g a t e d Mo.
I--
The following can be c o n c l u d e d f r o m t h e s e r e s u l t s :
T h e P induced t e m p e r 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 of
(b)
.~-$4 C r - M o s t e e l s d e p e n d s on the c o n c e n t r a t i o n s of Mo and
Cr d i s s o l v e d in the f e r t i l e m a t r i x . T h e s e , in t u r n ,
v:~ 2 a r e d e t e r m i n e d by the b u l k c o n c e n t r a t i o n s of Cr and
w
13_ ~ Mo and by the p r e c i p i t a t i o n of c a r b i d e s . T h e d o m i n a n t
r o l e of Mo is to s c a v e n g e P and thus to inhibit s e g r e -
gation, while that of C r is to e n h a n c e P s e g r e g a t i o n .
(c)
~4
(.9
E f f e c t of T i n
2 T i n is a v e r y p o w e r f u l e m b r i t t l e r in the N i - C r
t ; I i I
s t e e l s 33 due to the s t r o n g N i - S n c o s e g r e g a t i o n . How-
0 02 0.4 0.6 08 I0 1~2 14 e v e r , the Sn induced e m b r i t t l e m e n t in N i - C r s t e e l s
s e e m s to be s u p p r e s s e d b y Mo, p e r h a p s b y the s a m e
TOTAL M0 CONTENT(wt%) m e c h a n i s m a s for P . F o r e x a m p l e , W a d a 34 showed
Fig. 1 4 - A u g e r p e a k h e i g h t ratios from - 1 0 0 ~ fracture surfaces of that the t r a n s i t i o n t e m p e r a t u r e shift (A0) a f t e r s t e p
the step-cooled 2 8 8 Cr steels w i t h varying t o t a l Mo c o n t e n t : (a)
cooling for a m a r t e n s i t i c 3.5 N i - l . 7 C r - 0 . 1 V s t e e l
Pl2o/FeTo3, (b) Mots6/FeTo3, (c) Crs29/Fe~o 3 .
(with 0.25 C and 0.02 Sn) can be r e d u c e d f r o m ~ 250
f r o m z e r o , the d i s s o l v e d Mo c o n c e n t r a t i o n i n c r e a s e s to 50~ by the a d d i t i o n of 0.5 Mo.* T h i s i s a v e r y
and P is s c a v e n g e d . Although the i n c r e a s e d t e m p e r - *The specimens had the hardness level o f R c 35 and a grain size of ASTM
ing t i m e c a u s e s M7C3 to be f o r m e d at the e x p e n s e of No. 7.
M~C, the d o m i n a n t effect i s M o - P s c a v e n g i n g , and the p o w e r f u l d e m o n s t r a t i o n of the Mo effect, p a r t i c u l a r l y
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 d e c r e a s e s . When the Mo in the p r e s e n c e of Ni which can enhance the d r i v i n g
content i s r a i s e d beyond 0.7 pct, M2C r e p l a c e s MTCs, f o r c e for Sn s e g r e g a t i o n e n o r m o u s l y . A s i m i l a r r e -
i n c r e a s i n g the d i s s o l v e d Cr content and the e m b r i t t l e - s u l t was r e p o r t e d by Schulz ~5 f o r a 3.5 N i - l . 7 Cr
m e n t s u s c e p t i b i l i t y again r i s e s due to the c o s e g r e g a - steel.
l i o n of C r and P . The s a m e heat t r e a t m e n t s a s u s e d for the P doped
The A u g e r a n a l y s e s of the above s a m p l e s a r e c o n - s t e e l s w e r e e m p l o y e d for the 0.02 and 0.04 Sn s t e e l s .

Sn -DOPED STEELS, FINE G S

LOW HARDNESS INTERMEDIATE HARDNESS HIGH HARDNESS

- 25 I [ I -25 / ] I I -25 I I I
n 9 004 % 9 004% 9 004%
[] 002% r-t 0 0 ; ' %
w
t- -50 - -50 [ ] 002%
-50 t
z
o
I-- -75 -75
Z Q
<[
13
-JOO= - - 9 lJ-----
-I00 t -IOOL
[]
Fig. 1 5 - V a r i a t i o n w i t h aging time
o f the 4 ft-lb (5.4 J) t r a n s i t i o n tO -125 I [ I -125 ~ [ I I -125 I I ]
t e m p e r a t u r e and hardness of the 0 I 2 3 0 I 2 3 o I 2 3
fine grained 0.02 and 0.04 Sn
steels at three hardness levels, 320 I I I 320 - - I f 320 I I I
aged at 520~ W
rl
t~
v
280 280 - - 2801
(,9
bJ 240 240 ~B- - 240
Z
t3
IZ
200 k.....~. .~ _
2O0 - 200 --

160 I I L ~600 I I [ 160 I I I

I 2 3 2 I 3 t 2 3

AGEING TIME AT 5 2 0 ~ (103h)

284-VOLUME I 1 A , F E B R U A R Y 1980 METALLURGICAL TRANSACTIONS A

 The v a r i a t i o n of the t r a n s i t i o n t e m p e r a t u r e and m a t r i x
IVIOI a IVIO
h a r d n e s s at the fine g r a i n s i z e a r e given in F i g . 15.
F o r both s t e e l s A0 i s found to be v e r y s m a l l , with at
m o s t v e r y s l i g h t e m b r i t t l e m e n t in the f i r s t 50 h and -X~o) + ( X zp
aCrV~ Cr- X BC r '\ [2]
a f t e r that a s t e a d y s t a t e . M e t a l l o g r a p h i c e x a m i n a t i o n
of the a s - q u e n c h e d 0.04 Sn s t e e l by use of the s p e c i a l o _ X~ B
p i c r i c a c i d e t c h a n t which a t t a c k s P e n r i c h e d g r a i n Z~GMo = AGMo 2 a F e M o ( M o - X M o )
b o u n d a r i e s r e v e a l e d s o m e p e n r i c h m e n t in the g r a i n
b o u n d a r i e s . T h i s m a y account for the minute e m b r i t - ,
+ aMop(X P
r _ X~) + Or'
MoCr
( X q~
Cr - X c r )
B [3]
t l e m e n t which did o c c u r .
T h e X - r a y a n a l y s e s of the a s - t e m p e r e d H, I, and L
Sn doped s p e c i m e n s showed that the t y p e s of c a r b i d e AGCr = AG~r _ 2aFeCr(X~r _ XcrB )
present were:
H : M3C + ~Crp(Xp
' ~ - Xp) + aMoCr(XMo-- XMo) [4]
I: MzC + MTCa
L : M2C + MTCa T h e c o e f f i c i e n t s ~ij g i v e the net e n e r g y g a i n f r o m
f o r m i n g ij a t o m p a i r s at the e x p e n s e of ii and jj p a i r s ,
which i s the s a m e a s in the P s t e e l s . T h i s i s u n d e r - and the a ' c o e f f i c i e n t s give the e n e r g y gain when two
s t a n d a b l e b e c a u s e the p r e s e n c e of r e s i d u a l P o r 0.02 of t h r e e s o l u t e e l e m e n t s p a i r - u p at the e x p e n s e of the
to 0.04 Sn should not change s i g n i f i c a n t l y the c a r b i d e o t h e r two p o s s i b l e u n l i k e - a t o m p a i r i n g s . F o r e x a m p l e ,
p r e c i p i t a t i o n k i n e t i c s o r the c o n c e n t r a t i o n of Mo in OtFe p is p r o p o r t i o n a l to EFe p -- 1 / 2 ( E F e F e + c p p )
s o l u t i o n . T h e r e f o r e , the amount of Mo in s o l u t i o n for w h e r e ei] is the e n e r g y a s s o c i a t e d with the bond of an
the a g e d I o r L s p e c i m e n s would be ~ 0.4 p c t . Yet, ij a t o m p a i r , and O~MoP = a M o P - (OtFe P + O~FeMo).
t h e r e i s no e m b r i t t l e m e n t . In t h i s " q u a s i - c h e m i c a l " m o d e l the i n t e r n a l e n e r g y
Hence we can conclude that, in the a b s e n c e of Ni, of the s o l i d s o l u t i o n is a p p r o x i m a t e d by the s u m of
0.4 pct Mo in s o l u t i o n i s s u f f i c i e n t to s c a v e n g e 0.04 the e n e r g i e s of the n e a r e s t - n e i g h b o r b o n d s . B e c a u s e
pct Sn. We cannot s a y which f a c t o r i s m o r e i m p o r t a n t : of this s i m p l i f i c a t i o n , one cannot t a k e the m o d e l too
the a b s e n c e of Ni o r the M o - S n s c a v e n g i n g e f f e c t . l i t e r a l l y and e x p e c t to c a l c u l a t e a c c u r a t e l y X ~ (T)
using a and ~ ' v a l u e s o b t a i n e d f r o m h e a t s of f o r m a -
DISCUSSION
tion of p u r e c o m p o u n d s , o r s o m e o t h e r e m p i r i c a l
C o m p a r e d with the r e l a t i v e l y s i m p l e N i C r s t e e l s on m e t h o d . H o w e v e r , the r e g u l a r s o l u t i o n m o d e l i s of
which m o s t of the s y s t e m a t i c s t u d i e s of t e m p e r e m - g r e a t v a l u e for c o n c e p t u a l p u r p o s e s and for c o m p a r -
b r i t t l e m e n t have b e e n c a r r i e d out, C r M o s t e e l s ing the i n t e r a c t i v e e f f e c t s of v a r i o u s e l e m e n t s , a s
c l e a r l y offer a h i g h e r l e v e l of c o m p l e x i t y . F r o m the w i l l be s e e n h e r e .
p r e s e n t study, a s w e l l a s o t h e r r e l a t e d work, ~ it a p - F r o m Eq. [1] it can be s e e n that the m o s t i~paportant
p e a r s that P i s the only one of the c o m m o n i m p u r i t i e s q u a n t i t i e s f o r the d e t e r m i n a t i o n of X ~ a r e X ~ and
which p r o d u c e s a s i g n i f i c a n t a m o u n t of e m b r i t t l e m e n t . AGp. Since P is r e a s o n a b l y s u r f a c e - a c t i v e in F e ,
Although t h i s in i t s e l f s i m p l i f i e s the p r o b l e m , the AG~ is s i g n i f i c a n t (Eq. [2]), but we a l s o e x p e c t s u b -
c o m p l e x i t i e s a r i s e f r o m the e f f e c t s of v a r i a t i o n of s t a n t i a l c o n t r i b u t i o n s to AG,p f r o m the t e r m s in Eq.
the d i s s o l v e d Mo o r C r l e v e l s (due to c a r b i d e r e a c - [2] containing a M o P and a C r P . P a s t work29,~~ 39
t i o n s ) on the t e n d e n c y for s e g r e g a t i o n of P . T h e s e has i n d i c a t e d a s t r o n g a t t r a c t i v e i n t e r a c t i o n b e t w e e n
v a r i a t i o n s depend on the t h e r m a l h i s t o r y of the s t e e l C r and P and a v e r y s t r o n g a t t r a c t i o n b e t w e e n Mo
d u r i n g both heat t r e a t m e n t and s u b s e q u e n t e x p o s u r e
to aging(e.g., o p e r a t i n g ) t e m p e r a t u r e s . I I I I I
The t e r n a r y r e g u l a r solution m o d e l of G u t t m a n n ~
v
IAGED520~
c a n be g e n e r a l i z e d to p r o v i d e a f r a m e w o r k with which
to r a t i o n a l i z e the b e h a v i o r of 2.25 C r - 1 Mo s t e e l in a o 25
I--
q u a l i t a t i v e way. The e q u i l i b r i u m c o n c e n t r a t i o n of any rr i
p a r t i c u l a r solute in an i n t e r f a c e (which is t r e a t e d a s
a s e p a r a t e phase ~) i s given b y : 3v -r"
20-

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.

METALLURGICAL TRANSACTIONS A VOLUME l l A , F E B R U A R Y 1 9 8 0 - 2 8 5

 I I I I I I I I I I

o
50 O p

<[
rr

I : m
9 9
oom
9
9

<9 oO 9 9 9 Fig. 17-Relationship between

bJ 9"::. ",)r the intergranular concentrations
I

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 -
gation of Mo + P and Cr + P; hence, the t h r e e (X/~
--X B) would a l l i n c r e a s e and there would be mutual
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 -
fore, unless X~ were somehow d e c r e a s e d , an i n c r e a s e
in bulk concentration of Cr or Mo would be expected to
produce enhanced P s e g r e g a t i o n .
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
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-
tent r e t a r d it. The l a t t e r can be seen in F i g . 16 where
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
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
d e c r e a s e s as the Mo concentration in the f e r r i t e in-
c r e a s e s . This can only happen if Mo acts as a s c a v e n -
g e r of P and l o w e r s the mobile P concentration so
much that the ,large LxGp is m o r e than offset by the
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 .
Since the Mo does not scavenge all of the P, one
would expect to see some c o s e g r e g a t i o n of Mo and Cr
with the r e m a i n i n g P. This is supported by Fig. 17
which shows that both the Cr and Mo Anger peak
heights i n c r e a s e with the P peak height. Since n e i t h e r
Cr nor Mo a r e surface active in Fe to any a p p r e c i a b l e
extent, this behavior indicates c o s e g r e g a t i o n . It is not
p o s s i b l e to say how much Mo and Cr have c o s e g r e -
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 -
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 i n t e r p r e t a t i o n of the effects of Cr and Mo is
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
on the effects of v a r i o u s alloy e l e m e n t s on the solu-
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
shown that Mo i n t e r a c t s much more strongly with P
in Fe than does Cr. T h e i r r e s u l t s a r e consistent with
the p r e c i p i t a t i o n of some kind of Mo phosphide. It
should be noted that Nb, Ti, and Zr should be even
more potent P s c a v e n g e r s than Mo. The scavenging
of P by Ti was indicated by e a r l i e r work of Ohtani
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
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
Yen. 41 More r e c e n t work by DiDio and G r a h a m 42 has
d e m o n s t r a t e d the P scavenging effect of Mo by use of
the s a m e technique.
If it is a s s u m e d that the Mo + P scavenging effect
is the r e s u l t of the formation of Mo3P and that Mo3P
and Fe3P can f o r m a continuous, isomorphous solid
solution, then Guttmann's 43 adaptation of H i l l e r t ' s 44
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
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
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
given by :
exp(4.97 - 4490/T) [5]
X~
1 + [exp 5 5 3 6 / T - - 1]Xffr 3
B
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
a s - t e m p e r e d conditions and calculate X~, we can plot
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
t e m p e r a t u r e s (usingEq. [5]) as shown ifi F i g . 19. It
can be seen that this calculation is consistent with
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
is r e d u c e d significantly below the bulk concen-
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 -
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.)
The a s - t e m p e r e d values of X~ obtained above can
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
p a r a m e t e r s can be made to calculate X~ for the e a r l y
stage of segregation at 520~ When this was done, ~8
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-
tions was found to be 0.54 to 0.57, which is obviously
too s m a l l to explain the d i f f e r e n c e s found here in the
e m b r i t t l e m e n t behavior
~k (see F i g . 4(a)). In addition,
a calculation of X ~ vs t e m p e r a t u r e indicated that the
steep t e m p e r a t u r e dependence of X~p would occur above
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 -

2 8 6 - V O L U M E 11A, FEBRUARY 1980 METALLURGICAL TRANSACTIONS A

 I / T xlO-* t h i s was found in the effect of T i in a low C N i C r s t e e l
10.07 8 9 I0 II 12 doped with Sb. ~ The s t e e l was c o m p a r e d with and
a I I ~ ' f
8.0 without a T i addition and in the f o r m e r it was found
6,0 1 that some T i had c o s e g r e g a t e d with the Sb, d i s p l a c i n g
~ ~. ~-Fe-P Binary system s o m e of the Ni which n o r m a l l y c o s e g r e g a t e s with Sb.
4,0
F u r t h e r m o r e , the i n c r e a s e in t r a n s i t i o n t e m p e r a t u r e
for a given a m o u n t of s e g r e g a t e d Sb was c o n s i d e r a b l y
~I 2.0
t5 s m a l l e r in the s t e e l c o n t a i n i n g the s e g r e g a t e d T i .
08 C l e a r l y , the s u b s t i t u t i o n of T i for Ni in the g r a i n
.s I,O 06
0.8
b o u n d a r y made the Sb m u c h l e s s e m b r i t t l i n g .
04 An analogous effect of Mo on P has b e e n r e p o r t e d
= 0.6
o
by D u m o u l i n and G u t t m a u n47 b a s e d on a study of CrMo
,= 0.4 s t e e l s of c o m p o s i t i o n s d i f f e r e n t f r o m the ones studied
u)
0.2
o h e r e . Since t h i s would be a n a d d i t i o n a l b e n e f i c i a l ef-
0.2 Q_ fect of Mo to go along with the s c a v e n g i n g effect found
h e r e , we a t t e m p t e d to d e t e r m i n e whether or not it oc-
0,1 c u r r e d in our s t e e l s . The data f r o m the Wada and
~, 0.08 ,_~ , N j ~---~"'_, 0,04 Hagel s p e c i m e n s a r e s u m m a r i z e d in F i g . 20, and it
:.: 0.06 can be s e e n that the change in t r a n s i t i o n t e m p e r a t u r e
~ 0,04
_\ ,- p e r unit P s e g r e g a t i o n is not influenced by the c o n -
o ~r ~Nb ~\ \ " 0,02 c e n t r a t i o n of d i s s o l v e d Mo. We do not have data for
s e g r e g a t e d Mo b e c a u s e of the p r o b l e m of s e p a r a t i n g
0.02
I100 I000 900 800 700 600 500 the A u g e r s i g n a l f r o m s e g r e g a t e d Mo f r o m that due
Temperature (%) to i n t e r g r a n u i a r c a r b i d e s . However, s i n c e the d i s -
(a) solved Mo r e m a i n s e s s e n t i a l l y c o n s t a n t in the r a n g e
of t o t a l Mo b e t w e e n 0.7 and 1.3 pet, and s i n c e the s e g -
r e g a t e d P l e v e l in this r a n g e i n c r e a s e s , one would e x -
pect that the s e g r e g a t e d Mo c o n c e n t r a t i o n would not
fall to z e r o in this r a n g e . Yet the P potency h e r e a p -
p e a r s to be the s a m e a s in the Mo f r e e s t e e l . Since
the p r e s e n c e of c o s e g r e g a t e d C r m a y d i s t o r t this p i c -
t u r e c o n s i d e r a b l y , we can only say at p r e s e n t that we
' ' ' 1,o have yet to find e v i d e n c e to support a n effect of Mo on
the potency of P . However, on p h y s i c a l g r o u n d s ~ such
a n effect could be a n t i c i p a t e d .
F i n a l l y , the effect of p r i o r heat t r e a t m e n t on s u b -
s e q u e n t t e m p e r e m b r i t t l e m e n t can be d e m o n s t r a t e d

-oz_ , k ' ' ' ' A

o

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.

METALLURGICALTRANSACTIONSA VOLUME llA, FEBRUARY 1980-287

 I I if the 1a activity is high enough, r e m o v a l of Mo f r o m
solution by c a r b i d e f o r m a t i o n can offset a v e r y l a r g e
softening effect.
o.. I00 It should be noted that a p p a r e n t l y anomalous effects

~0~0/
/ 0 " - ' - ' 0 -

of h a r d n e s s on the kinetics and d e g r e e of t e m p e r e m -

b r i t t l e m e n t of other Mo containing s t e e l s , n a m e l y
-r 0
12. NiCrMoV and CrMoV r o t o r s t e e l s , have been o b s e r v e d
0
b e f o r e . 48,49 These effects a r e g e n e r a l l y consistent
f~
with the p r e s e n t r e s u l t s , and t h e r e f o r e we b e l i e v e that
u_ I0 they can be i n t e r p r e t e d b e s t not in t e r m s of h a r d n e s s
rE, --0
--r __ or m i c r o s t r u c t u r e alone, but by a l s o taking into account
the concentrations of Mo and Cr in the f e r r i f e ~hase.
This point was a l s o alluded to by Viswanathaa. 8

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

by an e x p e r i m e n t c a r r i e d out with s a m p l e s of the

9 0.o4 P
s t e e l s doped with 0.02 and 0.04 pet P and with 0.04
pet Sn. Since Sn is innocuous in this s t e e l , the Sn 9 0,02 P
9 0 04 Sn
doped s t e e l can be c o n s i d e r e d equivalent to an undoped n- ,~o , JI I I , ,
heat with the r e s i d u a l 0.002 pet P.* The s a m p l e s were
b.l
l.- 0 ~ ~
*However, it is not unhkely that the presence of the Sn would raise the
acUvity of this P, assumingSn to act hke Si (See Part II).
z
a u s t e n i t i z e d for 2 h at 1170~ t e m p e r e d for v a r i o u s n,-
-50
I.-
t i m e s at 650~ and e m b r i t t l e d by the common s t e p -
cooling t r e a t m e n t 29 As seen in F i g . 21(b), a l l t h r e e
s t e e l s softened with time at 650~ this in i t s e l f should -I00 I L I ,
lead to a reduction in t r a n s i t i o n t e m p e r a t u r e , a s is
found for the 0.02 P and the 0.04 Sn s a m p l e s . However, 350 (b) l 1 I I ,
A
the 0.04 P s a m p l e exhibits a maximum in e m b r i t t l e -
ment s u s c e p t i b i l i t y for a t e m p e r i n g t i m e of 10 h at
300
650~ According to the Baker and Nutting data
(Fig. 1) the 10 h t e m p e r i n g introduces the maximum - _-

amount of M2C, and the c a r b i d e is r e p l a c e d by M7C3 250

with f u r t h e r t e m p e r i n g . X - r a y a n a l y s i s of the above
s a m p l e s showed that the types of c a r b i d e p r e s e n t
were: I I I I

Tempering Time Carbide Type

rr
20 min MsC
"I-
Q.
20 t
1 h MsC
I0 h M2C + MvC~
IO
20 h M2C + M7C3 MOSTLY
O
CLEAVAGE
I
Thus, in the s t e e l containing 0.04 P the e m b r i t t l e m e n t t~ ia"
" "I I I I
in the s a m p l e t e m p e r e d for 10 H is g r e a t e r than the 0 I0 20
e m b r i t t l e m e n t in the h a r d e r (20 min and 1 h) s a m p l e s
TEMPERING TIME AT 6 5 0 * C ( h )
because of the r e m o v a l of Mo f r o m its P scavenging
Fig. 21-Variation with tempering time of the 4 ft-lb (5.4 J) transition
r o l e due to M2C f o r m a t i o n . T e m p e r i n g for 20 h p r o - temperature, hardness, and P12o/FeTo3 Auger peak height ratio from
duces even f u r t h e r softening, which finally s u c c e e d s - 1 0 0 ~ fracture surface of the step-cooled 0.04 P, 0.02 P, and 0.04
in reducing the e m b r i t t l e m e n t level somewhat. Thus, Sn steels.

288-VOLUME 11A, FEBRUARY 1980 METALLURGICAL TRANSACTIONS A

the dissolved Mo content remains constant and the dis-
solved Cr content increases.
These results have a number of implications which
should be recognized by users of steels containing Mo.
First, studies of temper embrittlement which do not
take account of the variations in dissolved Mo (and
Cr) due to variations in thermal history are liable to
be misinterpreted. Secondly, if steels containing 1
pct Mo are to be used in situations where temper em-
brittlement is possible, then the heat treatment (and
perhaps the carbon content) should be altered so as
to prevent formation of M2C at the expense of M7C3.
Finally, efforts should be made to improve the r e s i s -
tance of this class of steels to temper embrittlement
by basic changes in the alloy content and heat treat-
ment. The guiding principle should be to maximize
the concentration of dissolved Mo (or other effective
P scavengers, such as Nb) and to avoid precipitation
of Mo in carbides. Since Cr enhances P segregation
and is not an effective P scavenger (at least at the
concentrations examined here), increases in Cr should
be made with caution.
ACKNOWLEDGMENTS
This paper is based on work supported by the
National Science Foundation, MRL PrOgram, under
Grant No. DMR76-80994. In its initial phase support
was also received from the Commonwealth of Penn-
sylvania Science and Engineering Foundation. We are
particularly grateful to Drs. T. Wada and W. C. Hagel
of the Climax Molybdenum Co. for providing us with
specimens from their research and for helpful dis-
cussions. R. Stockdale, D. Schumacher, and R. Binns
of the Climax Molybdenum Co. performed the chemical
analysis of the electrolytes for Cr and Fe and some
of the analyses for Mo. At Pennsylvania Christine
McMahon carried out some of the Mo analyses and
the centrifuge separations. M s s r s . Shin-Cheng Fu and
H. Katz were of great assistance with the Auger and
X - r a y analyses, respectively.
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V O L U M E I1A, F E B R U A R Y 1 9 8 0 - 2 8 9