Mechanisms of Tempered Martensite

Embrittlement in Low Alloy Steels

R. M. HORN AND ROBERT O. RITCHIE

An i n v e s t i g a t i o n into the m e c h a n i s m s of t e m p e r e d m a r t e n s i t e e m b r i t t l e m e n t (TME),

a l s o know as "500~ ' ' or "350~ ' ' or o n e - s t e p t e m p e r e m b r i t t l e m e n t , has b e e n made
in c o m m e r c i a l , u l t r a - h i g h s t r e n g t h 4340 and S i - m o d i f i e d 4340 (300-M) alloy s t e e l s ,
with p a r t i c u l a r focus given to the r o l e of i n t e r l a t h f i l m s of r e t a i n e d a u s t e n i t e . Studies
w e r e p e r f o r m e d on the v a r i a t i o n of i) s t r e n g t h and t o u g h n e s s , and ii) the morphology,
volume f r a c t i o n and t h e r m a l and m e c h a n i c a l s t a b i l i t y of r e t a i n e d a u s t e n i t e , as a function
of t e m p e r i n g t e m p e r a t u r e , following o i l - q u e n c h i n g , i s o t h e r m a l holding, and continuous
a i r cooling f r o m the a u s t e n i t i z i n g t e m p e r a t u r e . TME was o b s e r v e d as a d e c r e a s e in both
Klc and Charpy V - n o t c h i m p a c t e n e r g y after t e m p e r i n g a r o u n d 300~ in 4340 and 425~
in 300-M, w h e r e the m e c h a n i s m s of f r a c t u r e w e r e e i t h e r i n t e r l a f h cleavage o r l a r g e l y
t r a n s g r a n u l a r cleavage. The e m b r i t t l e m e n t was found to be c o n c u r r e n t with the i n t e r -
lath p r e c i p i t a t i o n of c e m e n t i t e d u r i n g t e m p e r i n g and the c o n s e q u e n t m e c h a n i c a l i n s t a -
bility of i n t e r l a t h f i l m s of r e t a i n e d a u s t e n i t e d u r i n g s u b s e q u e n t loading. The r o l e of
s i l i c o n in 300-M was s e e n to r e t a r d these p r o c e s s e s and hence r e t a r d TME to higher
t e m p e r i n g t e m p e r a t u r e s than for 4340. The m a g n i t u d e of the e m b r i t t l e m e n t was found
to be s i g n i f i c a n t l y g r e a t e r in m i c r o s t r u c t u r e s c o n t a i n i n g i n c r e a s i n g v o l u m e f r a c t i o n s of
r e t a i n e d a u s t e n i t e . Specifically, in 300-M the d e c r e a s e in KIc, due to TME, was a 5
MPavCm i n oil quenched s t r u c t u r e s with l e s s than 4 pct a u s t e n i t e , c o m p a r e d to a m a s -
sive d e c r e a s e of 70 M P a v ~ in slowly (air) cooled s t r u c t u r e s c o n t a i n i n g 25 pct a u s t e n i t e .
A c o m p l e t e m e c h a n i s m of t e m p e r e d m a r t e n s i t e e m b r i t t l e m e n t is p r o p o s e d involving i)
p r e c i p i t a t i o n of i n t e r l a t h c e m e n t i t e due to p a r t i a l t h e r m a l d e c o m p o s i t i o n of i n t e r l a t h
f i l m s of r e t a i n e d a u s t e n i t e , and ii) s u b s e q u e n t d e f o r m a t i o n - i n d u c e d t r a n s f o r m a t i o n on
loading of r e m a i n i n g i n t e r l a t h a u s t e n i t e , d e s t a b i l i z e d by c a r b o n depletion f r o m c a r b i d e
p r e c i p i t a t i o n . The d e t e r i o r a t i o n in t o u g h n e s s , a s s o c i a t e d with TME, is t h e r e f o r e
a s c r i b e d to the e m b r i t t l i n g effect of i) i n t e r l a t h c e m e n t i t e p r e c i p i t a t e s and ii) an i n t e r -
lath l a y e r of m e c h a n i c a l l y - t r a n s f o r m e d a u s t e n i t e , i.e., u n t e m p e r e d m a r t e n s i t e . The
p r e s e n c e of r e s i d u a l i m p u r i t y e l e m e n t s in p r i o r a u s t e n i t e g r a i n b o u n d a r i e s , having
s e g r e g a t e d t h e r e d u r i n g a u s t e n i t i z a t i o n , m a y a c c e n t u a t e this p r o c e s s by p r o v i d i n g an
a l t e r n a t i v e weak path for f r a c t u r e . The r e l a t i v e i m p o r t a n c e of these effects is d i s -
cussed.

I T has b e e n well known for m a n y y e a r s that high a m b i e n t t e m p e r a t u r e Charpy V - n o t c h i m p a c t e n e r g y

s t r e n g t h m a r t e n s i t i c s t e e l s , h e a t - t r e a t e d to a c h i e v e
o p t i m u m c o m b i n a t i o n s of s t r e n g t h , ductility, and tough-
n e s s , a r e s u s c e p t i b l e to e m b r i t t l e m e n t d u r i n g t e m -
p e r i n g J -4 This l o s s in toughness can r e s u l t p r i m a r i l y
f r o m two types of t h e r m a l t r e a t m e n t s : i) holding or
slow cooling alloy s t e e l s , p r e v i o u s l y t e m p e r e d above
600~ in the t e m p e r a t u r e r a n g e 350 to 550~ ( t e m p e r
e m b r i t t l e m e n t ) , and ii) t e m p e r i n g a s - q u e n c h e d alloy
s t e e l s in the r a n g e 250 to 450~ ( t e m p e r e d m a r t e n s i t e
e m b r i t t l e m e n t ) . W h e r e a s t h e r e i s now a l a r g e body of
evidence l i n k i n g the p h e n o m e n o n of t e m p e r e m b r i t t l e -
m e n t to the g r a i n b o u n d a r y weakening effect of s e g r e -
gated i m p u r i t i e s or " t r a m p " e l e m e n t s (e.g., S, P, Sb,
Sn, and so forth1'2'4), the m e c h a n i s m of t e m p e r e d m a r -
t e n s i t e e m b r i t t l e m e n t (TME), also known as , ' 5 0 0 ~ ' '
or "350~ ' ' or " o n e - s t e p t e m p e r e m b r i t t l e m e n t " has
r e m a i n e d s o m e w h a t of a m y s t e r y . The e m b r i t t l e m e n t
has t r a d i t i o n a l l y b e e n s e e n as a sudden d e c r e a s e in
R. M. HORN is Associate Development Engineer, Department of
Materials Science and Mineral Engineering,University of California,
Berkeley, CA 94720. ROBERT O. RITCHIE is Associate Professor,
Department of MechanicalEngineering,Massachusetts Institute of
Technology, Cambridge, MA 02139. Both authors were formerly with
the Lawrence Berkeley Laboratory, University of California.
Manuscript submitted December 19, 1977.
ISSN 0360-2133/78/0810-1039500.75/0
METALLURGICALTRANSACTIONSA 9 1978AMERICANSOCIETYFOR METALSAND
THE METALLURGICALSOCIETYOF AIME
and an i n c r e a s e in the Charpy t r a n s i t i o n t e m p e r a t u r e
d u r i n g t e m p e r i n g , and was h i s t o r i c a l l y a s s o c i a t e d with
an i n c r e a s e in i n t e r g r a n u l a r f r a c t u r e d u r i n g failure.5-8
F r a c t u r e t o u g h n e s s and t e n s i l e ductility w e r e also s e e n
to be d e g r a d e d in c e r t a i n s t e e l s , but such m e a s u r e m e n t s
w e r e not always c o n s i s t e n t in r e v e a l i n g the e m b r i t t l e -
ment.~,9, I~
E a r l y e x p l a n a t i o n s of TME w e r e linked to the t r a n s -
f o r m a t i o n d u r i n g t e m p e r i n g of a u s t e n i t e , r e t a i n e d a f t e r
quenching. 11 However, this was l a r g e l y d i s c o u n t e d
s i n c e it was r e a l i z e d that i) r e f r i g e r a t i o n of the s t e e l
after quenching (which was p r e s u m e d to r e m o v e m o s t
of the r e t a i n e d a u s t e n i t e ) did not e l i m i n a t e the p h e n o m -
enon, v'12 and ii) t r a n s f o r m a t i o n of r e t a i n e d a u s t e n i t e
could not r e a d i l y a c c o u n t for the i n c i d e n c e of i n t e r -
g r a n u l a r f r a c t u r e which was o b s e r v e d . 5 However, l a t e r
work on higher alloy s t e e l s r e v e a l e d that f r a c t u r e s in
the e m b r i t t l e m e n t r a n g e w e r e not always i n t e r g r a n u l a r ;
m e c h a n i s m s such as cleavage, ~3'15 q u a s i c l e a v a g e , 9'~v
f i b r o u s , ~6 m i x e d d u c t i l e - b r i t t l e , ~4'4s m a r t e n s i t e " t r a n s -
l a t h " , 14 and m a r t e n s i t e ' ' i n t e r l a t h / / p a c k e t ''la f a i l u r e s
have been r e p o r t e d . G r o s s m a n n 5 was p r o b a b l y the f i r s t
author to s u g g e s t a m o r e definite link b e t w e e n the s e -
quence of c a r b i d e p r e c i p i t a t i o n and TME. This was
s u b s t a n t i a t e d by K l i n g e r and c o w o r k e r s s who found
VOLUME 9A, AUGUST 1978-1039
 that e m b r i t t l e m e n t was c o n c u r r e n t with the f o r m a t i o n
of p l a t e l e t c e m e n t i t e , r e p l a c i n g E - c a r b i d e , and that
TME was t i m e - d e p e n d e n t at d i f f e r i n g t e m p e r i n g t e m -
p e r a t u r e s , i . e . , t e m p e r i n g at l o n g e r t i m e s s o m e w h a t
below the c h a r a c t e r i s t i c e m b r i t t l i n g t e m p e r a t u r e a l s o
r e s u l t e d in e m b r i t t l e m e n t . T h i s t i m e - d e p e n d e n c e of
TME was f u r t h e r v e r i f i e d by s t u d i e s which showed
that r a p i d induction heating and cooling would s u p p r e s s
the e m b r i t t l e m e n t . 19 S e v e r a l o t h e r w o r k e r s r e l a t e d the
o n s e t of T M E to the f o r m a t i o n of c o a r s e n i n g of c e -
m e n t i t e f i l m s , which w e r e g e n e r a l l y o b s e r v e d to f o r m
at grain and lath boundaries.19-22 This important r o l e
of carbide precipitation on TME was supported by
work on high-strength steels modified with silicon and
aluminum.13'23-26 Both these elements are known to
retard the replacement of e-carbide by cementite to
higher tempering temperatures.26'2v It was found that
in such modified steels the embrittlement trough was
correspondingly displaced to higher temperatures.
Other authors suggested that a high dislocation density,
in addition to coarse carbide precipitation, was essen-
tial f o r e m b r i t t l e m e n t . 9'28'29 King e t a l . ~7 f u r n i s h e d
e v i d e n c e fo r this i n t e r a c t i o n by finding that the TME
t r o u g h was i n c r e a s e d to h i g h e r t e m p e r i n g t e m p e r a -
t u r e s in s t e e l s f r a c t u r e d below r o o m t e m p e r a t u r e .
B e c a u s e of the i n c i d e n c e of i n t e r g r a n u l a r f r a c t u r e
in many T M E f a i l u r e s , o t h e r t h e o r i e s of the p h e n o m e -
non have f o c u s s e d on the r o l e of g r a i n boundary s e g -
r e g a t i o n of r e s i d u a l i m p u r i t y e l e m e n t s . 3'3~ For ex-
a m p l e , it was found that alloying additions of c h r o m i u m
and m a n g a n e s e and the p r e s e n c e of c e r t a i n i m p u r i t y
e l e m e n t s , p h o s p h o r u s and n i t r o g e n , i n c r e a s e d the l e v e l
of e m b r i t t l e m e n t . 3~ Subsequently, the p r e s e n c e of s e g -
r e g a t e d P and N on TME i n t e r g r a n u l a r f r a c t u r e s u r -
f a c e s was d i r e c t l y i d e n t i f i e d using A u g e r s p e c t r o s -
copy. a2 H o w e v e r , the r o l e of i m p u r i t i e s on TME was
d e m o n s t r a t e d m o s t c o n v i n c i n g l y when t e s t s w e r e c o n -
ducted on I a b o r a t o r y - m a d e high p u r i t y s t e e l s of the
s a m e n o m i n a l c o m p o s i t i o n as s u s c e p t i b l e c o m m e r c i a l
s t e e l s , and the e m b r i t t l e m e n t p h e n o m e n o n w a s not ob-
s e r v e d at r o o m t e m p e r a t u r e * . T h i s p r o m p t e d B a n e r j i
of TME* in c o m m o n l y - u t i l i z e d c o m m e r c i a l u l t r a - h i g h
*This term willbe applied to the embrittlement phenomena observedrealizing
it is not unique to fully martensiticsteels.
s t r e n g t h s t e e l s . While we a c k n o w l e d g e that the e m -
b r i t t l e m e n t of a g i v en s t e e l cannot be a t t r i b u t e d to a
s i n g l e m e c h a n i s m , such as i n t e r l a t h c a r b i d e p r e c i p i -
tation, d e c o m p o s i t i o n of r e t a i n e d a u s t e n i t e , o r i m p u r i t y
s e g r e g a t i o n , and is a l m o s t c e r t a i n l y due to a c o m b i -
nation of s e v e r a l f a c t o r s , our a i m is to c l e a r l y d e m o n -
s t r a t e the r o l e of r e t a i n e d a u s t e n i t e as a m a j o r c o n t r i -
buting f e a t u r e in p r o m o t i n g the o n s e t of t e m p e r e d m a r -
tensite embrittlement.
EXPERIMENTAL PROCEDURES
The materials investigated were two commercial
ultra-high strength steels, AISI 4340 and 300-M, of
composition in weight percentages shown below:
C Mn Cr Ni Mo Si S P V Cu
4340 0.41 0.80 0.79 1.75 0.23 0.26 0.004 0.006 - 0.06
300-M 0.42 0.76 0.76 1.76 0.41 1.59 0.002 0.007 0.10 -
Th e c o m p o s i t i o n of 300-M is e s s e n t i a l l y that of 4340,
m o d i f i e d with 1.3 wt pct s i l i c o n . Both h eat s w e r e of
a i r c r a f t quality ( v a c u u m - a r c r e m e l t e d ) and w e r e r e -
c e i v e d as h o t - r o l l e d b a r in the fully annealed condition.
B e f o r e h e a t - t r e a t m e n t , a s - r e c e i v e d m a t e r i a l was hot
f o r g e d and hot r o l l e d to d e s i r e d t h i c k n e s s e s and s u b -
s e q u e n t l y s l o w - c o o l e d and s p h e r o i d i z e d at 650~ to
a c h i e v e good m a c h i n a b i l i t y . T e s t s p e c i m e n s w e r e
a u s t e n i t i z e d at 870~ for 1 h and then g i v en one of
t h r e e cooling t r e a t m e n t s (Fig. 1), n a m e l y i) d i r e c t
quenched in a g i t a t e d oil, ii) slow continuously cooled
at a r a t e e q u i v a l e n t to that e x p e r i e n c e d by 1 in. (25
m m ) or 2 in. (50 m m ) p l a t e d u r i n g a i r - c o o l i n g , or iii)
i s o t h e r m a l l y t r a n s f o r m e d by holding at 250~ * f or 1 h
*Isothermal holdingtemperature (250~ represents a transformation tempera-
ture of 50~ belowM s for 4340 and 20~ belowM s for 300-M

* Later work showedthat the TMEembrittlementtrough reappears for tests at b e f o r e o i l quenching ( e q u i v a l e n t to m a r t e m p e r i n g ) .

-196~ 47 T a b l e I l i s t s the cooling t r e a t m e n t s of i n t e r e s t f or
e t a l . 32 to p r o p o s e that the m e c h a n i s m of TME was the r e s p e c t i v e s t e e l s . T e s t s p e c i m e n s w e r e s u b s e -
e s s e n t i a l l y s i m i l a r to that of t e m p e r e m b r i t t l e m e n t , quently t e m p e r e d f o r 1 h in the t e m p e r a t u r e r a n g e 200
inv o l v i n g the s e g r e g a t i o n * of r e s i d u a l impur.ities, in
*Such segregationhas recentlybeen shown to occur during prior austenitiza-
tion,32,47 rather than during tempering,as is generallythe case for temperem-
brittlement.
this instance P and N, to prior austenite grain bound-
aries promoted by the co-segregation of Mn and pos-
sibly Si. Furthermore, attempts were made to ratio- v

~acr
_•
800
I

3~176
.......... ]
COOLINGPROFILE SCHEMATIC

94 ~ - CCT DIAGRAM
1

nalize a combined role of impurities and carbide pre-

cipitation by suggesting that during the growth of car- a:

bides, impurity elements are rejected giving rise to

t i12111
a local increase in impurity concentration at carbide/
matrix interfaces. More recently, attention has once 4o(3

more focused on the role of retained austenite on TME

based on new data concerning the distribution, mor-
phology, and thermal and mechanical stability of r e -
tained austenite during tempering.'3'18,a3 The objective 200
I0 I0 2 [0 3 IO 4
of the present investigation is to reassess this role TIME (SEC)
of retained austenite in the light of this new informa- Fig. 1-Schematic diagram displayingcoolingtreatments in-
tion, and to attempt to elucidate specific mechanisms vestigated on transformation diagram for 300-M steel.

1040-VOLUME 9A, AUGUST 1978 METALLURGICAL TRANSACTIONS A

to 650~ The prior austenite grain s i z e of all s t r u c - I I I I I
tures was a p p r o x i m a t e l y 20 ~tm. Ambient t e m p e r a t u r e It TENSILEPROPERTIES OF 300-M
300-- ~ ISOTHERMALLY TRANSFORMEDAT 250*C
uniaxial t e n s i l e p r o p e r t i e s w e r e d e t e r m i n e d using 25.4 -- 2000
m m gage length c y l i n d r i c a l and flat t e n s i l e b a r s , and
plane strain fracture toughness (KIc) v a l u e s w e r e d e -
t e r m i n e d using 25.4 m m thick 1 - T compact tension
iI~,,,,._9 T.S
s p e c i m e n s , in a c c o r d a n c e with appropriate ASTM s t a n - -

dards. Kic m e a s u r e m e n t s w e r e found to be valid, with 250

r e s p e c t to such standards, for all t e s t s except for

Table I. Heat-Treatments Investigated -- 1500

Cooling Treatment
Steel After Austenitization for 1 h at 870~ Designation 2OO
Yield
Stress
300-M Oil quenched 300-M-QT
300-M Isothermally held for 1 h at 250~ 300-M-ISO
300-M Slow continuously cooled to simulate air-cooling of 50 300-M-AC
turn thick plate
4340 Oil quenched 4340-QT
4340 Slow continuously cooled to simulate air cooling of 25 4340-AC 150
-- I000
mm thick plate 1 I I I
2OO 4OO 6O0
TEMPERING TEMPERATURE (*C)
(c)
350 I I I I I I
TENSILE PROPERTIES O F 300-M

35C 1 I I l I I

E Q~~ENc H ~ AISI 43~0

30C
!2000
co 2 5 0

25C

- - 1500 E
2OO 1500 o

Yield Stress"
\ \
150 150
--I000 OOO
I I I I I I
0 I00 200 300 400 500 600 700
TEMPERING TEMPERATURE (%)
- %
(a) I00
3O0
I t I ~00 I" M I I I I I 1 I I
TENSILE PROPERTIES OF :0OO 0 I00 200 300 400 500 600 700
AIR COOLED, 5.OCM THICK TEMPERING TEMPERATURE (~
(d)

2 5 C _e
250 1 I [ I I
.T.S.
TENSILE PROPERTIES OF AISI 4340
AIR COOLED, 2.5 CM THICK
ua 500
h 1500
zoc
200
A

150 AVERAGEDVALUES 2.....

9 SINGLETEMPER L~
tr
9 DOUBLETEMPER
DO0 150
I I I ] I I I000
0 IOO 200 3OO 400 500 600 700
TEMPERING TEMPERATURE (QC)
(b)
Fig. 2 - E f f e c t o f t e m p e r i n g t e m p e r a t u r e on the r o o m t e m p e r -
a t u r e u n i & x i a l t e n s i l e p r o p e r t i e s f o r heat t r e a t m e n t s i n v e s t i -
gated (a) o i l quenched 3 0 0 - M s t e e l , (b) a i r - c o o l e d , (50 m m I00 -
t h i c k s e c t i o n ) , 3 0 0 - M s t e e l , (c) i s o t h e r m a l l y - h e l d (at 250~ I I I I I I
i h), 3 0 0 - M s t e e l , (d) o i l - q u e n c h e d 4340 s t e e l , and (e) a i r - 0 IO0 200 300 400 500 600 700
c o o l e d (25 m m t h i c k s e c t i o n ) , 4340 s t e e l . ( A l l s t e e l s a u s t e n i - TEMPERING TEMPERATURE (~
t i z e d f o r 1 h at 870~ p r i o r to c o o l i n g . ) (e)

METALLURGICAL TRANSACTIONS A VOLUME 9A, AUGUST 1978-1041

specimens tempered at 650~ The toughness of the 300-M (300-M-QT) is shown in Fig. 3. Although in
latter structures was estimated using i) equivalent the a s - q u e n c h e d ( u n t e m p e r e d ) condition, the toughness
energy procedures at maximum load, a4 and ii) mea- is low (Kic = 35 M P a v ~ ) , the f r a c t u r e toughness i n -
surement of JIc values,3~ at initiation of fracture, de-
tected using the electrical potential method.3e ASTM
I ! I I I
standard Charpy V-notch impact tests were also con- 500-M- OIL QUENCHED
ducted to compare with fracture toughness results.
- Austenitized I hr at 870~ oil quenched, I00
All test specimens were machined in the longitudinal tempered for I hr
L-T orientation from rolled bar. QTin. C.TS.test specimen
Microstructures were characterized using optical I00
and transmission electron microscopy, and fracture
surface morphology was assessed using scanning elec-
tron microscopy. Levels of retained austenite in the 80
structures investigated were measured using stan-
dard X-ray techniques ~ and magnetic saturation in- 80
duction measurements.38 Volume fractions of austenite
determined by these two methods agreed to within •
pct. The mechanical stability of austenite, with r e - hi
50 (~
Z
spect to deformation, was assessed by continuously "r

monitoring the magnetic saturation of the steel during 0

uniaxial tensile tests. Calibration methods using aus- I--

tenite-free standards were utilized to determine initial

austenite levels. The distribution and morphology of I---

the retained austenite was characterized by standard 40

bright and dark field imaging with transmission elec- 9 "Valid" KIc results
tron microscopy. Carbide type was identified from
o "Invalid" K[creSults
from analysis39 of diffraction patterns of extraction
replicas taken from polished and over-etched metal-
lographic specimens. ZO
ZO 1 I I 1 I I
RESULTS 0 too z00 300 400 5OO 600 7oo
TEMPERING TEMPERATURE (QC)
The heat treatments investigated, namely oil quench- Fig. 3-Effect of tempering temperature on the room temper-
ing, air cooling, and isothermal holding after austenit- ature plane strain fracture toughness (K[c) of 300-M steel,
ization, are illustrated schematically in Fig. 1, and oil quenched.
are listed in Table I. Uniaxial tensile properties at
' I " I ] I l I I'''
ambient temperature for the five treatments are shown
-- 500-M ALLOY STEEL - QUENCHED AND TEMPERED
in Fig. 2 as a function of tempering temperature. Oil 60
Austenitized I hr at 870~ oil quenched, tempered for Ihr
quenched 300-M (300-M-QT) develops peak strength
after tempering at 300~ (Fig. 2(a)), and is significantly 4O
stronger than the air-cooled (300-M-AC) and isother-
mally-held (300-M-ISO) structures. Peak strength for 50
the latter treatments is also attained after tempering
I
at 300~ (Fig. 2(b) and (c)). AISI4340, of lower silicon
content than 300-M, develops a peak strength condition
after tempering at 200~ (Fig. 2(d) and (e)) with the oil 40
quenched structures (4340-QT) being significantly m
stronger than air-cooled structures (4340-AC). It is -.N
:E ;I1
apparent that the increased silicon content in 300-M
leads to i) higher overall strength levels than in 4340, 5 0 -<
due to solid solution strengthening and ii) a change in
the kinetics of tempering27 which shifts the optimum
i20
tempering temperature for peak strength from 200~
in 4340 to 300~ in 300-M*. Although tensile proper- 2O

*These tempering temperatures correspond to the commercially-used treatments

after oil quenching.
IO
ties v a r y c o n s i s t e n t l y with t e m p e r i n g t e m p e r a t u r e for
all t r e a t m e n t s , the n a t u r e of the cooling t r e a t m e n t has I0
a s i g n i f i c a n t i n f l u e n c e on m i c r o s t r u c t u r e and f r a c t u r e
p r o p e r t i e s . T h e s e effects a r e s u m m a r i z e d for the
individual treatments. O , I I 1 J 1 i I ~ l ~ I t 0
O IOO 200 300 400 500 6OO 700
A) 300-M S t e e l - O i l Quenching T r e a t m e n t ( 3 0 0 - M - Q T ) Asque~ched TEMPERING TEMPERATURE (~
Fig. 4-Effect of tempering temperature on the room temper-
The v a r i a t i o n of plane s t r a i n f r a c t u r e toughness ature Charpy V-notch impact energy of 300-M steel, oil
(Klc) with t e m p e r i n g t e m p e r a t u r e for o i l - q u e n c h e d quenched.

1042-VOLUME 9A, AUGUST 1978 METALLURGICAL TRANSACTIONS A

Fig. 5-Mechanisms of failure in 300-M steel, oil-quenched in (a) untempered condition showing a mixture of ductile rupture,
quasieteavage, and intergranular fracture, (b) tempered at 300~ displaying ductile rupture, (c) tempered at 400~ showing
transgranular cleavage with ductile rupture, and (d) tempered at 650~ displaying ductile rupture.
c r e a s e s r a p i d l y to 65 MPa~/-~ a f t e r t e m p e r i n g at 300~
T e m p e r i n g at a h i g h e r t e m p e r a t u r e of 400~ r e s u l t s in
a s l i g h t d e g r a d a t i o n in K I c , d e s p i t e the f a c t that the
s t r e n g t h is a l s o d e c r e a s i n g (Fig. 2(a)). T h i s " t o u g h n e s s
t r o u g h , " a l s o o b s e r v e d in C h a r p y V - n o t c h i m p a c t
e n e r g y d a t a (Fig. 4), i s an e x a m p l e of t e m p e r e d m a r -
t e n s i t e e m b r i t t l e m e n t (TME). Note, h o w e v e r , that the
e m b r i t t l e m e n t in the quenched and t e m p e r e d s t e e l r e -
s u l t s in only a s m a l l d r o p in t o u g h n e s s (~5 M P a ~ ) .
T e m p e r i n g at t e m p e r a t u r e s above 400~ l e a d s to a
s i g n i f i c a n t i n e r e a s e in t o u g h n e s s a s the s t r e n g t h of
the s t e e l d r o p s . The v a r i a t i o n of f r a c t u r e m o d e with
t e m p e r i n g t e m p e r a t u r e is shown in F i g . 5. A s - q u e n c h e d
s t r u c t u r e s f a i l e d by a m i x t u r e of d u c t i l e r u p t u r e ( m i -
c r o v o i d c o a l e s c e n c e ) , i n t e r g r a n u l a r and t r a n s g r a n u l a r
c l e a v a g e (Fig. 5(a)). S t r u c t u r e s t e m p e r e d at 300~
(the ' t o p ' of the TME trough), and at 400~ (the ' b o t -
t o m ' of the TME trough) f a i l e d by d u c t i l e r u p t u r e
(Fig. 5(b) and (c)), with s o m e e v i d e n c e of t r a n s g r a n u l a r
c l e a v a g e at 400~ F a i l u r e in s t r u c t u r e s t e m p e r e d at
650~ was b y 100 p e t d u c t i l e r u p t u r e (Fig. 5(d)).
The m i c r o s t r u e t u r e of o i l - q u e n e h e d 300-M, shown
in F i g . 6 for the a s - q u e n c h e d condition, was a m a r -
t e n s i t i c lath s t r u c t u r e , with s o m e twinning, and c o n -
t a i n e d e v i d e n c e of a l m o s t continuous thin f i l m s (100
to 200.~ thick) of r e t a i n e d a u s t e n i t e s u r r o u n d i n g the
METALLURGICAL TRANSACTIONS A
l a t h s . The h a r d e n i n g c a r b i d e was i d e n t i f i e d a s e - c a r -
b i d e at the 300~ condition, and c e m e n t i t e at t e m p e r i n g
conditions a b o v e 400~ The s t a b i l i t y of the r e t a i n e d
a u s t e n i t e was found to be a s t r o n g function of t h e r m a l
h i s t o r y and loading c o n d i t i o n s (Fig. 7). Shown in this
f i g u r e i s the v a r i a t i o n with t e m p e r i n g t e m p e r a t u r e of
the v o l u m e f r a c t i o n of r e t a i n e d a u s t e n i t e , m e a s u r e d
using m a g n e t i c s a t u r a t i o n techniques,* i) in the un-
*Initialvolumefractionsof austenitewere verifiedusingX-raytechniques,a7
s t r e s s e d m i c r o s t r u c t u r e , ii) a f t e r 0.2 p c t ( s t r a i n ( i . e . ,
at y i e l d ) , and iii) a f t e r 2 p c t s t r a i n . It is i m p o r t a n t at
this s t a g e to d i s t i n g u i s h b e t w e e n the v a r i a t i o n of the
p e r c e n t a g e of a u s t e n i t e in u n s t r e s s e d ( p r i o r to loading)
s t r u c t u r e s , which r e p r e s e n t s the " t h e r m a l s t a b i l i t y "
of r e t a i n e d a u s t e n i t e with r e s p e c t to t e m p e r i n g t e m -
p e r a t u r e , and the v a r i a t i o n of a u s t e n i t e p e r c e n t a g e
a f t e r s t r a i n , which r e p r e s e n t s the " m e c h a n i c a l s t a -
b i l i t y "" of r e t a i n e d a u s t e n i t e * with r e s p e c t to t e m p e r i n g
*Mechanicalstabilityas used refersto austenitestabilityto post-transformation
deformationas opposedto stabilizationby transformationstresses.
t e m p e r a t u r e . C o n s i d e r i n g f i r s t t h e r m a l s t a b i l i t y , it i s
a p p a r e n t that a p p r o x i m a t e l y 6 p c t is r e t a i n e d a f t e r oil
quenching, 4 p c t of which r e m a i n s t a b l e with t e m p e r i n g
up to t e m p e r a t u r e s of 400~ Above 470~ d e c o m p o s i -
tion of a u s t e n i t e d u r i n g t e m p e r i n g is e s s e n t i a l l y corn-
VOLUME 9A, AUGUST 1978-1043
 c u r s now at a r o u n d 470~ i s s t r i k i n g l y l a r g e r , i . e . , a
toughness d r o p of b e t w e e n 35 to 45 M P a 4 - ~ for t h e s e
c o n d i t i o n s c o m p a r e d with the 5 MPa4-m t o u g h n e s s
d r o p in the o i l - q u e n c h e d s t r u c t u r e s (Fig. 3). C h a r p y
V - n o t c h e n e r g y c u r v e s r e v e a l e d i d e n t i c a l t r e a d s . 13
F r a c t u r e m e c h a n i s m s w e r e s i m i l a r for the 3 0 0 - M - A C
and 3 0 0 - M - I S O t r e a t m e n t s . S t r u c t u r e s t e m p e r e d at
300~ (the ' t o p ' of the TME trough) f a i l e d by d u c t i l e
r u p t u r e , w h e r e a s at 470~ (the ' b o t t o m ' of the TME
trough) f a i l u r e o c c u r r e d by a lath b o u n d a r y c l e a v a g e
s e p a r a t i o n m e c h a n i s m (Fig. 10). Note the a b s e n c e of
i n t e r g r a n u l a r f r a c t u r e a s s o c i a t e d with TME, a s was
the c a s e for o i l - q u e n c h e d s t r u c t u r e s .
The m i c r o s t r u c t u r e s of the 3 0 0 - M - A C and 300-M-ISO
s t r u c t u r e s w e r e a l s o v e r y s i m i l a r , but s i g n i f i c a n t l y
d i f f e r e n t f r o m o i l - q u e n c h e d m a t e r i a l . Shown in F i g . 11
a r e b r i g h t and d a r k field e l e c t r o n m i c r o g r a p h s of the
3 0 0 - M - A C condition, a f t e r t e m p e r i n g at 300~ which
i n d i c a t e a p r i m a r i l y b a i n i t i c s t r u c t u r e containing a
l a r g e f r a c t i o n of t h i c k (~500/~) i n t e r t a t h f i l m s of r e -
t a i n e d a u s t e n i t e . The p r i n c i p a l h a r d e n i n g c a r b i d e for
both t r e a t m e n t s was i d e n t i f i e d a s ~ - c a r b i d e a f t e r t e m -
p e r i n g at 300~ and c e m e n t i t e at 470~ The t h e r m a l
and m e c h a n i c a l s t a b i l i t y of the a u s t e n i t e with r e s p e c t
to t e m p e r i n g t e m p e r a t u r e i s shown in F i g s . 12 and 13
for the 3 0 0 - M - A C and 3 0 0 - M - I S O t r e a t m e n t s , r e s p e c -
t i v e l y . It i s c l e a r that the v o l u m e f r a c t i o n of r e t a i n e d
a u s t e n i t e ( b e f o r e d e f o r m a t i o n ) in t h e s e s t r u c t u r e s i s
s i g n i f i c a n t l y g r e a t e r than in o i l quenched s t r u c t u r e s
( s e e Fig. 7), 13 to 16 p c t r e m a i n i n g s t a b l e up to t e m -
p e r i n g t e m p e r a t u r e s of 425~ Above this t e m p e r a t u r e ,
i n i t i a l a u s t e n i t e l e v e l s d e c r e a s e quite r a p i d l y a s d e -
c o m p o s i t i o n o c c u r s d u r i n g t e m p e r i n g at the h i g h e r
t e m p e r a t u r e s . The m e c h a n i c a l s t a b i l i t y of the a u s -

Fig. 6-Transmission electron microscopy of 300-M, direct

oil-quenched from 870~ showing retained austenite films
surrounding martensite laths: (a) bright field image and; (b)
dark field image of austenite reflection, showing contrast
reversal.

p l e t e . T h e m e c h a n i c a l s t a b i l i t y of the a u s t e n i t e , s e e n
by c o m p a r i n g u n s t r e s s e d l e v e l s with t h o s e a f t e r 0.2
and 2.0 p c t s t r a i n , i s s o m e w h a t d i f f e r e n t . It is c l e a r
that a u s t e n i t e p r e s e n t in the u n t e m p e r e d s t r u c t u r e i s
e x t r e m e l y u n s t a b l e , s i n c e a l l but 1 p c t of the o r i g i n a l
r e t a i n e d a u s t e n i t e h a s t r a n s f o r m e d by y i e l d (0.2 p c t
s t r a i n ) . M e c h a n i c a l s t a b i l i t y is l a r g e s t for t e m p e r i n g
t e m p e r a t u r e s a r o u n d 300 to 350~ but the r e t a i n e d
a u s t e n i t e b e c o m e s m e c h a n i c a l l y d e s t a b i l i z e d a g a i n at
400~ which c o r r e s p o n d s to the t e m p e r i n g t e m p e r a -
t u r e w h e r e TME o c c u r s .

B) 300-M S t e e l - A i r Cooling ( 3 0 0 - M - A C ) and

I s o t h e r m a l (300-M-ISO) T r e a t m e n t s
The v a r i a t i o n s in f r a c t u r e t o u g h n e s s with t e m p e r i n g
t e m p e r a t u r e f o r the 3 0 0 - M - A C and 3 0 0 - M - I S O t r e a t -
m e n t s a r e shown in F i g s . 8 and 9, i n d i c a t i n g s i m i l a r
t r e n d s to that e x h i b i t e d for the o i l - q u e n c h e d t r e a t m e n t
( 3 0 0 - M - Q T ) a s shown in F i g . 3. The p e a k t o u g h n e s s
v a l u e s a r e a g a i n a c h i e v e d a f t e r t e m p e r i n g at 300~
but a r e s i g n i f i c a n t l y h i g h e r ( K l c ~ 90 MPaV-m) c o n -
s i s t e n t with the fact that the a i r - c o o l e d and i s o t h e r - Fig. 7-Variation of percentage of retained austenite, measured
by magnetic saturation, with tempering temperatures for oiL-
m a l l y - t r a n s f o r m e d s t r u c t u r e s a r e of l o w e r s t r e n g t h . quenched, 300-M steel. Plotted are initial (unstressed) level
H o w e v e r , the m o s t s i g n i f i c a n t d i f f e r e n c e i s that the and amounts untransformed at 0.2 pct strain (i.e., at yield)
t e m p e r e d m a r t e n s i t e e m b r i t t l e m e n t trough, which o c - and at 2.0 pct strain.

1044-VOLUME 9A, AUGUST 1978 METALLURGICAL TRANSACTIONS A

tenite with r e s p e c t to t e m p e r i n g t e m p e r a t u r e is s i m i -
l a r for both 300-M-AC and 300-M-ISO t r e a t m e n t s , and
follows the s a m e t r e n d shown by o i l - q u e n c h e d s t r u c -
t u r e s (Fig. 7). In the u n t e m p e r e d state, r e t a i n e d a u s -
Fig. 8-Effect of tempering temperature on the room temper-
ature plane strain fracture toughness of 300-M steel, air-
cooled (50 mm thick plate).
Fig. 9-Effect of tempering temperature on the room temper-
ature plane strain fracture toughness of 300-M steel, iso-
thermally held at 250~ 1 h.
METALLURGICALTRANSACTIONSA
tenite is again u n s t a b l e m e c h a n i c a l l y (all 15 pct is
t r a n s f o r m e d by 2 pct s t r a i n in the 300-M-ISO condi-
tion), w h e r e a s after t e m p e r i n g at 300~ it b e c o m e s
v e r y stable. Marked m e c h a n i c a l d e s t a b i l i z a t i o n can
be s e e n to o c c u r at t e m p e r i n g t e m p e r a t u r e s above
425~ t e m p e r a t u r e s which a r e a s s o c i a t e d with the
o n s e t of t e m p e r e d m a r t e n s i t e e m b r i t t l e m e n t (Figs. 8
and 9). Thus, it is a p p a r e n t for 300-M s t e e l that the
s e v e r i t y of TME is d i r e c t l y r e l a t e d to the v o l u m e f r a c -
tion of r e t a i n e d a n s t e n i t e , and that o n s e t of the e m b r i t -
t l e m e n t c o i n c i d e s with the t e m p e r i n g t e m p e r a t u r e at
which a u s t e n i t e b e c o m e s m e c h a n i c a l l y u n s t a b l e with
r e s p e c t to d e f o r m a t i o n .
C) AISI 4340 S t e e l - O i l - Q u e n c h e d (4340-QT) and
A i r - C o o l i n g (4340-AC) T r e a t m e n t s
As a c o n s e q u e n c e of lower s i l i c o n content, the c h a r -
a c t e r i s t i c s of h e a t - t r e a t e d 4340 s t e e l a r e somewhat
d i f f e r e n t f r o m 300-M. In addition to exhibiting lower
s t r e n g t h l e v e l s , the v a r i a t i o n of toughness in 4340 with
t e m p e r i n g t e m p e r a t u r e , shown in Fig. 14 for the o i l -
quenched (4340-QT) condition and in Fig. 15 for the
a i r - c o o l e d (4340-AC) condition, has the s a m e g e n e r a l
t r e n d as that shown by 300-M. The t e m p e r a t u r e d e p e n -
dence of the b e h a v i o r , however, has shifted. This i s a
c o n s e q u e n c e of the r o l e of s i l i c o n 27 in 300-M, which
Fig. 10-Mechanisms of failure in 300-M, isothermally-held
and (a) tempered at 300~ showing ductile rupture and (b)
tempered at 470~ displaying interlath cleavage.
VOLUME 9A, AUGUST 1978-1045
 a u s t e n i t e a r e s i g n i f i c a n t l y l e s s than in 300-M ( m a x i -
m u m v o l u m e f r a c t i o n of 6 pct), and slow cooling a f t e r
a u s t e n i t i z i n g (i.e., with the 4340-AC t r e a t m e n t ) d o e s
not y i e l d i n c r e a s e d v o l u m e f r a c t i o n s as was the c a s e
for 300-M. The a u s t e n i t e is r e a s o n a b l y s t a b l e to t h e r -
maI d e c o m p o s i t i o n up to t e m p e r i n g t e m p e r a t u r e s of
200~ w h e r e u p o n its t h e r m a l and m e c h a n i c a l s t a b i l i t y
d e c r e a s e s r a p i d l y . D e s p i t e the shift to l o w e r t e m p e r i n g
t e m p e r a t u r e s c a u s e d by the l o w e r s i l i c o n content c o m -
p a r e d to 300-M, the s m a l l m a g n i t u d e of the TME
t r o u g h is c o n s i s t e n t with the s m a l l e r o v e r a l l l e v e l s of
r e t a i n e d a u s t e n i t e , and the t e m p e r i n g t e m p e r a t u r e for
the o n s e t of TME again c o i n c i d e s with d e s t a b i l i z a t i o n
of the a u s t e n i t e .

Fig. l l - T r a n s m i s s i o n electron microscopy of 300-M, air-

cooled and tempered at 300*C, showing retained austenite
films on bainitic-martensitic matrix: (a) bright field image;
and (b) dark field image of austenite reflection reversing
contrast.

r e t a r d s the f o r m a t i o n of c e m e n t i t e and extends the

t e m p e r a t u r e at which z - c a r b i d e e x i s t s . A c c o r d i n g l y ,
peak s t r e n g t h and t o u g h n e s s in 4340 a r e a c h i e v e d a f t e r Fig. 12-Variation of percentage of retained austenite, mea-
t e m p e r i n g at 200~ i n s t e a d of at 300~ in 300-M, and sured by magnetic saturation, with tempering temperature
the TME trough, which can be s e e n to be p a r t i c u l a r l y for 300-M, air-cooled. (Unstressed. 0.2 pct strain, 2 pct
s m a l l , i s s i m i l a r l y d i s p l a c e d to l o w e r t e m p e r i n g t e m - strain levels shown.)
p e r a t u r e s around 275~ Charpy V-notch energy m e a -
s u r e m e n t s r e v e a l e d i d e n t i c a l t r e n d s . *a Table II. Summary of Tempered Mertensite Embrittlement Phenomena
The f r a c t u r e m e c h a n i s m s of s t r u c t u r e s t e m p e r e d at
200~ and 275~ (the ' t o p ' and ' b o t t o m ' of the TME Tempering
trough, r e s p e c t i v e l y ) , a r e shown in Fig. 16 for the Tempering Maximum Regimefor
Steeland Regimefor Toughness Austenite Austenite
4340-AC s t r u c t u r e . At 200~ f a i l u r e o c c u r s by d u c t i l e Treatment Embrittlement Drop,MPa-v/-m Destabilization Level,Pet
r u p t u r e with i s o l a t e d c l e a v a g e f a c e t s (Fig. 16(a)), w h e r e -
as at 275~ the e m b r i t t l e d s t r u c t u r e f a i l s by a fully 300-M ~400oc 5 >~400~ 5
Oil quenched
t r a n s g r a n u l a r c l e a v a g e m e c h a n i s m (Fig. 16(b)); no 300-M
e v i d e n c e of i n t e r g r a n u l a r c r a c k i n g was again d e t e c t e d . Isothermally ~425~ 30 ~>400~ 12
A n a l y s i s of the m i c r o s t r u c t r e s in 4 3 4 0 - Q T showed held at 250~
that, a s with 300-M s t e e l , the h a r d e n i n g c a r b i d e at 300-M
peak s t r e n g t h and t o u g h n e s s (i.e., a f t e r 200~ t e m p e r ) 50 mm, air ~450~ 40 ~>425~ 14
cooled
was c - c a r b i d e , w h e r e a s in the T M E t r o u g h (i.e., a f t e r 300-M
t e m p e r i n g at 275~ c e m e n t i t e was d e t e c t e d . Thin 100 mm, air ~450~ 70 ~>425~ 25
i n t e r l a t h f i l m s of r e t a i n e d a u s t e n i t e w e r e p r e s e n t cooled
within a lath m a r t e n s i t i c s t r u c t u r e . 49 4340 ..~275OC 5 ~>250~ 5
The t h e r m a l and m e c h a n i c a l s t a b i l i t y of r e t a i n e d Oil quenched
4340
a u s t e n i t e with r e s p e c t to t e m p e r i n g t e m p e r a t u r e is 25 ram, air ~275~ 5 ~>275~ 4
shown in F i g s . 17 and 18 for the 4340-QT and 4340-AC cooled
t r e a t m e n t s , r e s p e c t i v e l y . C l e a r l y o v e r a l l l e v e l s of

1046-VOLUME 9A, AUGUST 1978 METALLURGICAL TRANSACTIONS A

 DISCUSSION ' I ~ I ~ I ~ I ~ I ' I i

AISI 4 3 4 0 - A I R COOLED, 2.5CM THICK

A s d e s c r i b e d i n t h e I n t r o d u c t i o n to t h i s p a p e r , t h e 12C
Austenitized l hr ot 870~ pit cooled,
currently held views on tempered martensite embrit-
tlement are that the embrittlement is associated with IO0
t h e p r e c i p i t a t i o n of c e m e n t i t e ~'s'ls-== a n d / o r t h e s e g r e -
g a t i o n of r e s i d u a l i m p u r i t y e l e m e n t s , ~,~~ and that the
o r i g i n a l e x p l a n a t i o n s b a s e d o n t h e d e c o m p o s i t i o n of I0(3
r e t a i n e d a u s t e n i t e h a v e b e e n l a r g e l y d i s c o u n t e d ~'~='~~

I I I I I 8O
:E
20 300-M ALLOY STEEL-ISOTHERMALLY TRANSFORMED-
AT 250~ 8C o
v
Austenitized Ihr at 870~ held at 250~ Ihr, oil cooled, _
18
tempered for Ihr (~
Prior to loading o3
hi

16 - - . e - - At yield (e =0.002)
- - - o---At 2 % strain ( e = 0,0 2)
== ~ 6c
F-
o 14
W
IX
I--
J2
4O
W
~ 40
(,') I0 9 "Valid" Ktc results
/ I
/ I o "Invalid" KIc results
r'~ // p, I
,,, 8 - // /" "\
_z
/ /" "\.
/
I--- / /" \ 20- 2O
"' 6 -- / = I L I L I L I I i I I I
/ / R 0 lOG 200 :300 400 500 600 700
/ / /" TEMPERING TEMPERATURE (~

\'\
_ /
/ /" Fig. 15-Effect of t e m p e r i n g t e m p e r a t u r e on the r o o m t e m p e r -
/ a t u r e plane s t r a i n f r a c t u r e toughness of 4340 steel, a i r cooled
/ /
(25 m m thick section).
2
/
o r forgotten. H o w e v e r , it i s quite c l e a r f r o m the p r e s -
0 -d
ent study that, depending on the t h e r m a l and m e c h a n i -
I J I J I
0 K)O 200 300 400 500 600 cal s t a b i l i t y of the a u s t e n i t e with r e s p e c t to t e m p e r i n g
TEMPERIN G TEMPERATURE (~ t e m p e r a t u r e in 4 3 4 0 - t y p e s t e e l s , the p r e s e n c e of r e -
Fig. 1 3 - V a r i a t i o n of p e r c e n t a g e of r e t a i n e d austenite, with t a i n e d a u s t e n i t e can p l a y a m a j o r r o l e in the o n s e t and
t e m p e r i n g t e m p e r a t u r e for 300-M, i s o t h e r m a l l y - h e l d at s e v e r i t y of the e m b r i t t l e m e n t ( T a b l e 1]). F o r each
250~ 1 h. ( U n s t r e s s e d , 0.2 pct s t r a i n , 2.0 pct s t r a i n levels
shown. ) h e a t - t r e a t m e n t s c h e d u l e i n v e s t i g a t e d in both s t e e l s ,
the o n s e t of TME c o i n c i d e s d i r e c t l y with the r a n g e of
I l I [ I I
t e m p e r i n g t e m p e r a t u r e at which r e t a i n e d a u s t e n i t e b e -
4340 ALLOY STEEL-QUENCHED~LND TEMPERED ! c o m e s m e c h a n i c a l l y u n s t a b l e with r e s p e c t to d e f o r m a -
Austenitized I hr at 870"C, oil quenched,
tion. Changing the s i l i c o n content of the s t e e l , which
tempered for I hr c h a n g e s the k i n e t i c s of c a r b i d e p r e c i p i t a t i o n , has no
effect on t h i s c o r r e l a t i o n ; the TME t r o u g h s t i l l o c c u r s
~ lOC o v e r the t e m p e r i n g t e m p e r a t u r e r a n g e w h e r e a u s t e n i t e
b e c o m e s u n s t a b l e . F u r t h e r m o r e , the m a g n i t u d e of the
e m b r i t t l e m e n t , in t e r m s of the~ s i z e of the d e c r e a s e in
-- 80
Kic, is d i r e c t l y p r o p o r t i o n a l to the a m o u n t of r e t a i n e d
a u s t e n i t e p r e s e n t . Thus, a i r - c o o l e d and i s o t h e r m a l l y -
t r a n s f o r m e d s t r u c t u r e s , with t h e i r h i g h e r v o l u m e
f r a c t i o n s of r e t a i n e d a u s t e n i t e , show s i g n i f i c a n t l y
l a r g e r TME t r o u g h s than o i l - q u e n c h e d s t r u c t u r e s ,
~.
despite the fact that s u c h s t r u c t u r e s a r e of l o w e r
s t r e n g t h (Fig. 2). To t e s t this f u r t h e r , s p e c i m e n s of
300-M w e r e v e r y s l o w l y c o n t i n u o u s l y c o o l e d to s i m u -
l a t e the a i r cooling of a 100 m m thick p l a t e , w h e r e e x -
olid" KIc results t r e m e l y high l e v e l s of a u s t e n i t e (~25 pct) a r e r e t a i n e d . 13
40 The r e s u l t i n g v a r i a t i o n in Kic with t e m p e r i n g t e m p e r a -
0 "Invalid" Kzc results
t u r e (Fig. 19) i n d i c a t e s a m a s s i v e TME trough, w h e r e
Kic d e c r e a s e s f r o m 110 MPa./-m at the ' t o p ' of the
I J I I I I trough (300~ t e m p e r ) to a m e r e 40 MPa~r-m at the
o I00 200 500 400 500 600 700
' b o t t o m ' (450~ t e m p e r ) . The o n s e t of this 70 MPa~rm
TEMPERING TEMPERATURE r
Fig. 14-Effect of t e m p e r i n g t e m p e r a t u r e on the r o o m t e m p e r - d e c r e a s e in t o u g h n e s s once a g a i n was found to c o i n -
a t u r e plane s t r a i n f r a c t u r e toughness of 4340 steel, oil cide with the t e m p e r i n g t e m p e r a t u r e r a n g e w h e r e r e -
quenched. tained a u s t e n i t e b e c o m e s m e c h a n i c a l l y u n s t a b l e , and
METALLURGICAL TRANSACTIONS A VOLUME 9A, AUGUST 1978-t047
 a g a i n no e v i d e n c e of i n t e r g r a n u l a r f a i l u r e w o u l d b e
d e t e c t e d in e m b r i t t l e d s a m p l e s . 13 C l e a r l y , m e c h a n i c a l l y
d e s t a b i l i z e d r e t a i n e d a u s t e n i t e c a n n o t b e d i s m i s s e d as
one of the r o o t c a u s e s of T M E , and f o r 4 3 4 0 - t y p e s t e e l s ,
the e x p l a n a t i o n b a s e d on r e t a i n e d a u s t e n i t e m u s t b e
reevaluated.
E a r l y i n v e s t i g a t i o n s 7'x2 d i s c o u n t e d the r o l e of r e -
t a i n e d a u s t e n i t e on T M E b e c a u s e i) r e f r i g e r a t i o n
t r e a t m e n t s a f t e r a u s t e n i t i z i n g did not r e m o v e the
e m b r i t t l e m e n t , and if) the i n t e r g r a n u l a r c h a r a c t e r of
e m b r i t t l e d f r a c t u r e s u r f a c e s s e e n in low a l l o y c a r b o n

Fig. 18-Variation of percentage of retained austenite with

tempering temperature for 4340 steel, air cooled (unstressed,
Fig. 16-Mechanism of failure in 4340, air cooled (a) tempered 0.2 pct strain, 2.0 pet strain levels shown).
at 200~ displaying ductile rupture, and (b) tempered at 275~
displaying t r a n s g r a n u l a r cleavage.

Fig. 19-Effect of tempering t e m p e r a t u r e on the plane strain

Fig. 17-Variation of percentage of retained austenite with fracture toughness for 300-M steel, air-cooled to r e p r e s e n t
tempering t e m p e r a t u r e for oil-quenched 4340 steel (unstressed, 100 mm thick plate. (Note the 70 MPa~m drop in toughness
0.2 pet strain, 2.0 pet strain levels shown). after tempering at 450~

1048-VOLUME 9A, AUGUST 1978 METALLURGICAL TRANSACTIONS A

Fig. 2 0 - 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 of 300-M s t e e l oil quenched and t e m p e r e d at 400~ (a) Bright field image r e v e a l i n g
m a r t e n s i t i c lath s t r u c t u r e , (b) d a r k field image of (200).~ r e v e r s e s c o n t r a s t of austenite, (c) d a r k field image of (102) c e m e n t i t e
reflection r e v e r s e s contr_as_t of discontinuous c a r b i d e fiIrn at lath boundary, (d) diffraction p a t t e r n of [11t~11[010] Fe3C I1[011]~
zones. A is (200if, B is (102)Fe3C.

METALLURGICAL TRANSACTIONS A VOLUME 9A, AUGUST 1978-1049

s t e e l s could not be d i r e c t l y linked to the p r e s e n c e of
a u s t e n i t e . However, r e f r i g e r a t i o n p r o c e d u r e s xz (and,
i n c i d e n t a l l y , the c o m m e r c i a l l y - u s e d p r o c e d u r e of
double t e m p e r i n g .3) a r e only p a r t i a l l y s u c c e s s f u l in
r e m o v i n g a u s t e n i t e in low alloyed s t e e l s . * F u r t h e r -
*Theseaddedproceduresreduce the austenitelevelapproximately2 to 4 pet.
m o r e , it has b e e n c l e a r l y d e m o n s t r a t e d in the p r e s e n t
i n v e s t i g a t i o n and o t h e r s T M that i n t e r g r a n u l a r f r a c t u r e
is not n e c e s s a r i l y a c h a r a c t e r i s t i c of TME, p a r t i c u -
l a r l y in these c o m m e r c i a l l y i m p o r t a n t s t e e l s . In the
p r e s e n t study, the l a r g e s t e m b r i t t l e m e n t troughs in
s t r u c t u r e s c o n t a i n i n g s i g n i f i c a n t p r o p o r t i o n s of i n t e r -
l a t h a u s t e n i t e (300-M-AC and 300-M-ISO), w e r e a s -
s o c i a t e d with a n i n t e r l a t h c l e a v a g e m e c h a n i s m of
f a i l u r e (Fig. 10(b)), w h e r e a s the s m a l l e r TME troughs,
in s t r u c t u r e s with low a u s t e n i t e content (300-M-QT,
4340-QT and 4340-AC) w e r e a s s o c i a t e d with t r a n s -
g r a n u l a r cleavage (Fig. 16(b))or m i x e d c l e a v a g e / m i -
crovoid c o a l e s c e n c e (Fig. 5(c)) f a i l u r e s . The fact that
no i n t e r g r a n u l a r f r a c t u r e was evident in e m b r i t t l e d
s a m p l e s in the p r e s e n t s t e e l s is not to d i s c o u n t the
r o l e of i m p u r i t i e s on TME, s i n c e c o a r s e r g r a i n e d
s t r u c t u r e s may well give r i s e to s o m e i n t e r g r a n u l a r
f a i l u r e , 32 but m e r e l y s e r v e s to e m p h a s i z e that i m p u r i t y
effects a r e not n e c e s s a r i l y a d o m i n a n t c a u s e of TME.
Fig. 21-Transmission electron microscopy of 300-M steel,
air cooled and tempered at 470~ (a) Bright field image of
bainitic-martensite matrix containing retained austenite and
cementite. (b) Dark field image of (200)/ reflection reversing
contrast of austenite.
1050-VOLUME9A, AUGUST 1978
The other i m p o r t a n t f e a t u r e of TME a p p a r e n t f r o m
the p r e s e n t work was that, for a l l t r e a t m e n t s studied,
E - c a r b i d e , identified as the h a r d e n i n g c a r b i d e at peak
s t r e n g t h (and c o n c u r r e n t peak toughness), was r e p l a c e d
by c e m e n t i t e in the e m b r i t t l e m e n t r a n g e . F u r t h e r m o r e ,
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 of e m b r i t t l e d s t r u c -
t u r e s (Fig. 20) r e v e a l e d that the c e m e n t i t e had p r e c i p -
itated as d i s c o n t i n u o u s i n t e r l a t h f i l m s (Fig. 20(c)).
Other a u t h o r s have a t t r i b u t e d the TME trough d i r e c t l y
to i n t e r l a t h c e m e n t i t e p r e c i p i t a t i o n . Thus, it is a p p a r -
ent that the o n s e t of TME c o i n c i d e s both with mechani-
cal d e s t a b i l i z a t i o n of i n t e r l a t h f i l m s of a u s t e n i t e , and
the r e p l a c e m e n t of c - c a r b i d e by p r e c i p i t a t i o n of i n t e r -
lath c e m e n t i t e . T h e s e two p h e n o m e n a a r e c l e a r l y
linked, s i n c e the c a r b i d e is p r e c i p i t a t i n g in the s a m e
location a s f i l m s of high c a r b o n a u s t e n i t e . This is
shown in Fig. 20 w h e r e d a r k field i m a g i n g of the lath
s t r u c t u r e in e m b r i t t l e d 3 0 0 - M - Q T (i.e., t e m p e r e d at
400~ v e r i f i e s the simultaneous p r e s e n c e of a u s t e n i t e
and c e m e n t i t e on i n t e r l a t h b o u n d a r i e s . It is, t h e r e f o r e ,
c o n s i d e r e d that the s e q u e n c e of TME is as follows.
A u s t e n i t e is r e t a i n e d as i n t e r l a t h f i l m s in a s - c o o l e d
s t r u c t u r e s (e.g., F i g u r e 7) due to m e c h a n i c a l s t a b i l i -
zation and t h e r m a l s t a b i l i z a t i o n f r o m slight p a r t i t i o n -
ing of c a r b o n d u r i n g a u s t e n i t i z i n g in o i l - q u e n c h e d
s t r u c t u r e s , or is r e t a i n e d in l a r g e r p r o p o r t i o n s due
to s i g n i f i c a n t c a r b o n p a r t i t i o n i n g d u r i n g a i r - c o o l i n g
o r i s o t h e r m a l holding in s l o w - c o o l e d s t r u c t u r e s . This
high c a r b o n a u s t e n i t e on lath b o u n d a r i e s can then act
as a p r i m a r y s o u r c e for the p r e c i p i t a t i o n and growth
of e m b r i t t l i n g c a r b i d e f i l m s at a u s t e n i t e - m a r t e n s i t e
lath i n t e r f a c e s . * Once the c a r b i d e f o r m s , the a u s -
*It has beenrecentlyshowns~that cementiteis precipitateddirectlyfrom
austenitein silicon-containingbainiticsteels.
tenite b e c o m e s depleted in c a r b o n , and a c c o r d i n g l y
b e c o m e s m e c h a n i c a l l y u n s t a b l e . T a b l e HI l i s t s the
a u s t e n i t e l a t t i c e p a r a m e t e r (ao) for 300-M-AC in dif-
f e r e n t t e m p e r conditions. After t e m p e r i n g at 470~
the a u s t e n i t e has e x p e r i e n c e d a d e c r e a s e in a 0 con-
s i s t e n t with c a r b o n depletion. On d e f o r m a t i o n , the
u n s t a b l e a u s t e n i t e t r a n s f o r m s to l e a v e an e m b r i t t l i n g
film of u n t e m p e r e d m a r t e n s i t e on lath b o u n d a r i e s , in
the s a m e location as the e m b r i t t l i n g c e m e n t i t e p r e c i p i -
tates. It is not p o s s i b l e f r o m the p r e s e n t study to d i s -
c u s s the r e l a t i v e c o n t r i b u t i o n s to the s e v e r i t y of TME
f r o m t h e s e two e m b r i t t l i n g effects. However, we would
p o s t u l a t e that i n s t r u c t u r e s c o n t a i n i n g s m a l l volume
f r a c t i o n s of r e t a i n e d a u s t e n i t e , such as 3 0 0 - M - Q T ,
4340-QT, and 4340-AC, the e m b r i t t l i n g effect of the
i n t e r l a t h c a r b i d e s is d o m i n a n t . This is c o n s i s t e n t
with the f r a c t u r e mode o b s e r v e d in e m b r i t t l e d s a m p l e s
of these s t r u c t u r e s which is p r i m a r i l y t r a n s g r a n u l a r
cleavage (Fig. 16), p r e s u m a b l y i n i t i a t e d by the t e n s i l e
c r a c k i n g of g r a i n b o u n d a r y or i n t e r l a t h c a r b i d e s . In
s t r u c t u r e s c o n t a i n i n g l a r g e v o l u m e f r a c t i o n s of r e -
Table III. Austenite Lattice Parameter for 300-M-AC After Tempering
Tempering
Treatment Austenite,Pet ao(311)3' ao(220)3'
300~ 13.2 3.627A 3.628A
400~ 14.6 3.611A 3.616A
470~ 3.2 3.598A 3.598A
METALLURGICALTRANSACTIONSA
 m e c h a n i c a l d e s t a b i l i z a t i o n of a d j a c e n t f i l m s of r e t a i n e d
rained a u s t e n i t e , h o w e v e r , such a s 3 0 0 - M - A C and
a u s t e n i t e (due to c a r b o n d e p l e t i o n ) a s a c o n s e q u e n c e of
300-M-ISO, the f r a c t u r e m o d e in e m b r i t t l e d s a m p l e s
this c a r b i d e p r e c i p i t a t i o n , and iii) the e m b r i t t l i n g effect
is i n t e r l a t h c l e a v a g e , which s u g g e s t s that the e m b r i t -
of a consequent l a y e r of m e c h a n i c a l l y - t r a n s f o r m e d
fling effect of the l a y e r of m e c h a n i c a l l y - t r a n s f o r m e d
a u s t e n i t e ( i n t e r l a t h u n t e m p e r e d m a r t e n s i t e ) . The r o l e
a u s t e n i t e (i.e., u n t e m p e r e d m a r t e n s i t e ) i s d o m i n a n t ,
of i m p u r i t e i s is not r u l e d out a s a m e c h a n i s m for TME,
c o n s i s t e n t with the m a r k e d l y i n c r e a s e d s e v e r i t y of
s i n c e if the l e v e l of r e s i d u a l ' t r a m p ' e l e m e n t s i s s u f -
TME in t h e s e s t r u c t u r e s . Thus, a m e c h a n i s m i s p r o -
f i c i e n t l y high, s u c h e l e m e n t s m a y be a l r e a d y p r e s e n t
p o s e d for t e m p e r e d m a r t e n s i t e e m b r i t t l e m e n t in u l t r a -
in p r i o r a u s t e n i t e g r a i n b o u n d a r i e s due to s e g r e g a t i o n
high s t r e n g t h s t e e l s which r e l i e s on i) the p r e c i p i t a t i o n
d u r i n g a u s t e n i t i z a t i o n 3e'47 p r o v i d i n g a l t e r n a t i v e ' e a s y
and growth of e m b r i t t l i n g c e m e n t i t e f i l m s on g r a i n and
p a t h s ' for f a i l u r e . S e p a r a t i o n would p r e s u m a b l y i n i t i -
i n t e r l a t h b o u n d a r i e s and ii) the c o n c u r r e n t t h e r m a l and
ate at w e a k e n e d g r a i n b o u n d a r y c a r b i d e / m a t r i x i n t e r -
f a c e s l e a d i n g to i n t e r g r a n u t a r f r a c t u r e s . H o w e v e r , it
a) TRANSGRANULAR CLEAVAGE a p p e a r s for the p r e s e n t s t r u c t u r e s that i m p u r i t y e f -
f e c t s a r e of s e c o n d a r y i m p o r t a n c e .
T h o m a s is has r e c e n t l y p r o p o s e d that the s p e c i f i c
r o l e of r e t a i n e d a u s t e n i t e on TME is the thermal d e -
s t a b i l i z a t i o n of a u s t e n i t e at the e m b r i t t l i n g t e m p e r i n g
t e m p e r a t u r e r e s u l t i n g in t h e r m a l t r a n s f o r m a t i o n to
i n t e r l a t h c a r b i d e . T h i s , h o w e v e r , i s only p a r t i a l l y
c sltiiltlOundary correct since untransformed austenite is still present
in unstressed e m b r i t t l e d s t r u c t u r e s ( s e e F i g s . 7, 12,
13, 17 and 18). This is c l e a r l y v e r i f i e d in F i g . 21,
grain boundary which shows the p r e s e n c e of r e t a i n e d a u s t e n i t e f i l m s
in 3 0 0 - M - A C t e m p e r e d at 470~ (i.e., at the ' b o t t o m '
of the TME t r o u g h in Fig. 8). The i m p o r t a n t fact is
that, although a c e r t a i n f r a c t i o n of the a u s t e n i t e d o e s
t r a n s f o r m t h e r m a l l y d u r i n g t e m p e r i n g to f o r m i n t e r -
b) INTERLATH CLEAVAGE lath c a r b i d e , the l a r g e r p r o p o r t i o n r e m a i n s t h e r m a l l y
s t a b l e , but m e c h a n i c a l l y u n s t a b l e , due to c a r b o n d e p l e -
mechanically unstable tion, and then t r a n s f o r m s on s u b s e q u e n t loading.
rlath austenite
In the context of the p r e s e n t w o r k and p r e v i o u s r e -
s e a r c h on a wide r a n g e of s t e e l s 1'a3'47'48 we a r e now
a b l e to p r o p o s e m e c h a n i s m s for TME which account
for the o b s e r v e d e m b r i t t l e m e n t f r a c t u r e m e c h a n i s m s ;
namely, transgranular cleavage, interlath cleavage,
intergranular cracking, ductile rupture, or mixed mode.
T h e s e a r e s c h e m a t i c a l l y i l l u s t r a t e d in F i g . 22. It i s
c l e a r that the e s s e n t i a l f e a t u r e of TME i s e m b r i t t l e -
ment from cementite precipitation during tempering.
In high s t r e n g t h s t e e l s , such a s 4340, t h i s o c c u r s on
g r a i n and lath b o u n d a r i e s , aided by t h e r m a l d e c o m p o -
s i t i o n of i n t e r l a t h f i l m s of a u s t e n i t e . In s t e e l s w h e r e
c) INTERGRANULAR CRACKING
the l e v e l of i m p u r i t i e s and r e t a i n e d a u s t e n i t e i s s m a l l ,
residual impurity elements the d o m i n a n t e m b r i t t l e m e n t m e c h a n i s m i s the t e n s i l e
from segregation to prior
austenite grain boundaries f r a c t u r e of s u c h c a r b i d e s and the r e s u l t i n g f r a c t u r e
. ing austenitization m o d e will be t r a n s g r a n u l a r c l e a v a g e (i.e., 4340-QT
and 4340-AC). H o w e v e r , the c o n s e q u e n c e of i n t e r l a t h
c a r b i d e p r e c i p i t a t i o n i s m e c h a n i c a l d e s t a b i l i z a t i o n of
the r e m a i n i n g i n t e r l a t h a u s t e n i t e , r e s u l t i n g in l a r g e l y
s t r e s s - a s s i s t e d t r a n s f o r m a t i o n to an i n t e r l a t h l a y e r of
u n t e m p e r e d m a r t e n s i t e . T h i s p r o v i d e s an i n c r e a s i n g l y
m a j o r c o n t r i b u t i o n to e m b r i t t l e m e n t in m i c r o s t r u c t u r e s
containing l a r g e r v o l u m e f r a c t i o n s of a u s t e n i t e , r e s u l t -
ing in an i n t e r l a t h c l e a v a g e f r a c t u r e m o d e (i.e.,
300-M-ISO and 3 0 0 - M - A C ) . In s t e e l s containing s u f -
f i c i e n t r e s i d u a l i m p u r i t y content (i.e., i m p u r i t y - d o p e d
s t e e l s ) , o r m i c r o s t r u c t u r e s p a r t i c u l a r l y s u s c e p t i b l e to
Fig. 22-Schematic diagrams of mechanisms of tempered g r a i n b o u n d a r y e m b r i t t l e m e n t (i.e., c o a r s e - g r a i n e d
martensite embrittlement showing resultant fracture modes s t r u c t u r e s ) , such i m p u r i t i e s , p a r t i c u l a r l y P, will tend
due to: (a) eementite precipitation at lath and grain boundaries, to s e g r e g a t e to p r i o r a u s t e n i t e g r a i n b o u n d a r i e s d u r i n g
(b) cementite precipitation and films of mechanically unstable a u s t e n i t i z a t i o n . 32'47 In the e m b r i t t l e m e n t r a n g e , the
retained austenite at lath boundaries, and (c) cementite pre- c o m b i n a t i o n of c e m e n t i t e p r e c i p i t a t e s and i m p u r i t i e s
cipitation and residual impurity elements at prior austenite
grain boundaries. Cases (a), (b) or (c) tested at a tempera- in p r i o r a u s t e n i t e g r a i n b o u n d a r i e s will l e a d to the
ture above the ductile to brittle transition temperature may l o w e s t c o h e s i o n at g r a i n b o u n d a r y c a r b i d e / m a t r i x
exhibit ductile rupture or mixed mode. i n t e r f a c e s , r e s u l t i n g in i n t e r g r a n u l a r f r a c t u r e . Should

METALLURGICAL TRANSACTIONS A VOLUME 9A, AUGUST 1978-1051

the t e m p e r a t u r e of t e s t i n g be above the d u c t i l e / 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 i x e d mode o r f i b r o u s f r a c -
t u r e s m a y r e s u l t in the TME r a n g e . T h i s is c o n s i s t e n t
with r e s u l t s that show, for c e r t a i n s t e e l s , no TME at
a m b i e n t t e m p e r a t u r e , y e t m a r k e d e m b r i t t l e m e n t at
-196~ 47 and f r a c t o g r a p h i c o b s e r v a t i o n s in the e m -
b r i t t l e m e n t r a n g e of m i x e d f i b r o u s / i n t e r g r a n u l a r f r a c -
t u r e at a m b i e n t t e m p e r a t u r e and 100 p c t i n t e r g r a n u l a r
f r a c t u r e at -196~ 48
It is concluded that TME in a given s t e e l cannot be
g e n e r a l l y a t t r i b u t e d to a s i n g l e m e c h a n i s m , and in
many c a s e s a l l t h r e e m e c h a n i s m s ; n a m e l y t h o s e i n -
volving c a r b i d e p r e c i p i t a t i o n , u n s t a b l e a u s t e n i t e and
i m p u r i t y s e g r e g a t i o n , m a y act in c o n c e r t , the r e s u l t -
ant f r a c t u r e m o d e m e r e l y i n d i c a t i n g the w e a k e s t path.
It i s felt, h o w e v e r , that the p r e s e n t work, while con-
f i r m i n g that the e s s e n t i a l f e a t u r e of TME is c e m e n t i t e
p r e c i p i t a t i o n , c l e a r l y d o c u m e n t s the fact that the p r e s -
ence of i n t e r l a t h f i l m s of r e t a i n e d a u s t e n i t e can m a r k -
edly a f f e c t the s e v e r i t y of this e m b r i t t l e m e n t .
CONCLUDING REMARKS
T h e r e h a s b e e n m u c h d i s c u s s i o n r e c e n t l y on the
b e n e f i c i a l r o l e of r e t a i n e d a u s t e n i t e on the t o u g h n e s s
of a l l o y s t e e l s , such a s 434018'4~ It is a p p a r e n t f r o m
the p r e s e n t p a p e r , h o w e v e r , that b e f o r e such c l a i m s
can be m a d e , it is e s s e n t i a l to d e f i n e the s t a b i l i t y of
the a u s t e n i t e both thermally and mechanically. With
r e s p e c t to T M E , t h e r m a l l y u n s t a b l e i n t e r l a l h a u s t e n i t e ,
with r e s p e c t to t e m p e r i n g t e m p e r a t u r e , is c l e a r l y not
b e n e f i c i a l , s i n c e the t r a n s f o r m a t i o n p r o d u c t is i n t e r -
lath c e m e n t i t e , a s s i m i l a r l y p r o p o s e d by T h o m a s . ~8
M o r e i m p o r t a n t l y , m e c h a n i c a l l y u n s t a b l e a u s t e n i t e , in
the p r e s e n t s t e e l s , * i s a l s o c l e a r l y not b e n e f i c i a l , s i n c e
*Large increases in toughness in higher alloyed steels (i.e., 10 pct Cr-9 pct Ni-5
pct Mo) of lower carbon content (0,2 pct) have been ascribed to the strain-induced
transformation of mechanically unstable austenite, (the basis of "TRIP" Steels4S).
The reasons for this marked difference in behavior compared to the present 4340-
type steels are most likely related to i) the transformation product in the higher
carbon 4340 steel will be a more brittle (higher carbon) martensite, and ii) the
embrittling effect of mechanically unstable austenite in 4340 steels occurs after
a principally stress-assisted transformation (i.e., a large proportion of the austenite
has transformed before yield); and iii) the transformation in the 4340-type steels
occurs in hardened, low-ductility matrix.
the t r a n s f o r m a t i o n p r o d u c t i s u n t e m p e r e d m a r t e n s i t e
which r e s u l t s in m a s s i v e e m b r i t t l e m e n t t r o u g h s (Figs~
9, 10, and 19). Since r e t a i n e d a u s t e n i t e i s s i m i l a r l y
m e c h a n i c a l l y u n s t a b l e in u n t e m p e r e d s t r u c t u r e s , we
would strongly question any claims1s'41'42 of an increase
in toughness due to the presence of retained austenite
in as-quenched steels, without evidence of its mechan-
ical stability.
The question also arises whether stable retained
austenite can be beneficial to toughness.* Several
* Related work on the influence of mechanically stable retained austenite on
other properties suggest that the presence of a continuous interlath network of
this phase in bainitic/martensitic structures in 300-M can significantly improve
resistance to stress-corrosion cracking when compared to quenched and tempered
structures, containing no austenite, at equivalent strength, 39 and marginally im-
prove resistance to very low growth rate, near-threshold, fatigue crack propagation
when compared at equivalent cyclic strength. 46
a u t h o r s ~s'41-44 have c l a i m e d this to be so, but c o m -
p a r i s o n s w e r e m a d e at d i f f e r e n t s t r e n g t h l e v e l s , ~s''~
b e t w e e n two d i f f e r e n t s t e e l s , '8 in u n t e m p e r e d s t e e l s , ~8'42
and in s t r u c t u r e s w h e r e o t h e r m i c r o s t r u c t u r a l c h a n g e s
w e r e not defined. 44 F u r t h e r m o r e , in no c a s e s w e r e the
t h e r m a l and m e c h a n i c a l s t a b i l i t i e s of the a u s t e n i t e u n -
1052-VOLUME 9A, AUGUST 1978
a m b i g u o u s l y d o c u m e n t e d . In the p r e s e n t i n v e s t i g a t i o n ,
a i r - c o o l e d o r i s o t h e r m a l l y - t r a n s f o r m e d 300-M, a f t e r
t e m p e r i n g a t 300~ i s s u b s t a n t i a l l y t o u g h e r than the
corresponding oil-quenched structure. Because these
t r e a t m e n t s l e a d to l a r g e v o l u m e f r a c t i o n s of r e t a i n e d
a u s t e n i t e and l o w e r s t r e n g t h , h o w e v e r , it can only be
concluded that the p r e s e n c e of m e c h a n i c a l l y s t a b l e
a n s t e n i t e d o e s not a p p e a r to i m p a i r p r o p e r t i e s . The
e v i d e n c e to f u r t h e r s u g g e s t that the p r e s e n c e of r e -
t a i n e d a u s t e n i t e l e a d s d i r e c t l y to t o u g h n e s s i n c r e a s e s
(without s t r e n g t h l o s s ) i s i n c o n c l u s i v e .
CONCLUSIONS
B a s e d on a study of the p h e n o m e n o n of t e m p e r e d
m a r t e n s i t e e m b r i t t l e m e n t (TME) in c o m m e r c i a l u l t r a -
high s t r e n g t h 4340 and S i - m o d i f i e d 4340 (300-M) a l l o y
s t e e l s s u b j e c t to quench and t e m p e r i n g , i s o t h e r m a l
t r a n s f o r m a t i o n and a i r - c o o l i n g h e a t - t r e a t m e n t s , the
following s p e c i f i c c o n c l u s i o n s can be m a d e :
1) TME is m a n i f e s t a s a d e c r e a s e in t o u g h n e s s ,
m e a s u r e d both in Kic and C h a r p y V - n o t c h i m p a c t
e n e r g y data, a f t e r t e m p e r i n g at a r o u n d 275~ in 4340
and a r o u n d 400 to 4~0~ in 300-M.
2) The e m b r i t t l e m e n t is c o n c u r r e n t with the r e p l a c e -
m e n t of c - c a r b i d e by i n t e r l a l h c e m e n t i t e d u r i n g t e m -
p e r i n g , and the m e c h a n i c a l i n s t a b i l i t y of i n t e r l a t h f i l m s
of a u s t e n i t e (as a c o n s e q u e n c e of this c a r b i d e p r e c i p i -
tation) d u r i n g s u b s e q u e n t loading.
3) The d i s p l a c e m e n t of TME to h i g h e r t e m p e r i n g
t e m p e r a t u r e s in 300-M, due to the i n c r e a s e d s i l i c o n
content, r e s u l t s f r o m the effect of t h i s e l e m e n t e n h a n c -
ing the s t a b i l i t y of E - c a r b i d e , r e t a r d i n g the f o r m a t i o n
and growth of c e m e n t i t e and c o n s e q u e n t l y i n c r e a s i n g
the t h e r m a l and m e c h a n i c a l s t a b i l i t y of r e t a i n e d a u s -
t e n i t e at h i g h e r t e m p e r i n g t e m p e r a t u r e s .
4) The s e v e r i t y of TME i s d i r e c t l y r e l a t e d to the
v o l u m e f r a c t i o n of i n t e r l a t h , r e t a i n e d a u s t e n i t e p r e s e n t .
I s o t h e r m a l l y - t r a n s f o r m e d and a i r - c o o l e d 300-M, c o n -
taining g r e a t e r than 12 p e t r e t a i n e d a u s t e n i t e , a r e
t h e r e f o r e s i g n i f i c a n t l y m o r e s u s c e p t i b l e to TME than
s t r u c t u r e s containing low v o l u m e f r a c t i o n s of a u s t e n i t e .
5) The m e c h a n i s m s of f r a c t u r e in e m b r i t t l e d s t r u c -
t u r e s was found to be i n t e r l a t h c l e a v a g e in m i c r o s t r u c -
t a r e s containing l a r g e p e r c e n t a g e s of i n t e r l a t h a u s -
t e n i t e (i.e~ which show s e v e r e e m b r i t t l e m e n t ) , and
transgranular cleavage or mixed cleavage/microvoid
c o a l e s c e n c e in m i c r o s t r u c t u r e s containing low p e r -
c e n t a g e s of a n s t e n i t e . No e v i d e n c e of i n t e r g r a n u l a r
c r a c k i n g was d e t e c t e d .
6) A new m e c h a n i s m of t e m p e r e d m a r t e n s i t e e m b r i t -
t l e m e n t i s p r o p o s e d involving i) p r e c i p i t a t i o n of i n t e r -
lath c e m e n t i t e a i d e d by p a r t i a l t h e r m a l d e c o m p o s i t i o n
of i n t e r l a t h f i l m s of r e t a i n e d a u s t e n i t e , and ii) s u b s e -
quent d e f o r m a t i o n - i n d u c e d t r a n s f o r m a t i o n on loading
of r e m a i n i n g i n t e r l a t h a u s t e n i t e , which has b e c o m e
m e c h a n i c a l l y u n s t a b l e due to c a r b o n d e p l e t i o n a s a
c o n s e q u e n c e of this c a r b i d e p r e c i p i t a t i o n .
In addition, the following g e n e r a l c o n c l u s i o n s on the
n a t u r e of TME can be m a d e :
1) The e s s e n t i a l f e a t u r e of TME i s the p r e c i p i t a t i o n
d u r i n g t e m p e r i n g of b r i t t l e c e m e n t i t e on g r a i n and l a t h
b o u n d a r i e s . Lath b o u n d a r i e s m a y a l s o contain l a y e r s
of m e c h a n i c a l l y - u n s t a b l e a u s t e n i t e , a s a c o n s e q u e n c e
of this c a r b i d e p r e c i p i t a t i o n , w h e r e a s g r a i n b o u n d a r i e s
may also contain residual impurity elements, as a con-
sequence of segregation during austenitization.
METALLURGICAL TRANSACTIONSA
 2) I n s t e e l s c o n t a i n i n g l a r g e v o l u m e f r a c t i o n s o f 13. R. M. Horn: Ph.D. Thesis, University of California at Berkeley, 1976 (Lawrence
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14. V, H. Lindborg and B. L. Averbach: ActaMet., 1966, vol. 14, p. 1583.
and mechanically unstable austenite on lath boundaries
! 5. E. F. Walker and M. J. May: ISI Publ. 120, p. 135, 1970.
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t l e m e n t r a n g e , a n d to t h e m o s t s e v e r e f o r m o f T M E . Fracture, Waterloo, vol. 2, p. 73, 1977.
3) I n s t e e l s w h i c h c o n t a i n s i g n i f i c a n t i m p u r i t y l e v e l s 17. J. E. King, R. F. Smith, andJ. F. Knott: 1bid, vol. 2, p. 279.
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19. A. Nakashirna and J. F. Libsch: Trans. ASM, 1961, vol, 53, p. 753.
embrittlement, the combination of cementite precipi-
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t e n i t e g r a i n b o u n d a r i e s l e a d s to f r a c t u r e b y i n t e r g r a n - Society for Testing and Materials, 1963.
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4) In steels containing small levels of austenite and (Lawrence Berkeley Laboratory Report No. LBL-405, November 1971).
23. A. G. Allten andP. Payson: Trans. ASM, 1953, vol. 45, p. 498.
impurities, the tensile cracking of brittle cementite
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precipitates o n g r a i n a n d l a t h b o u n d a r i e s l e a d s to 25. C. J. Ahstetter, M. Cohen, and B. L. Averbach: Ibid, 1962, vol. 55, p. 287.
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5) I n s t e e l s t e s t e d a t t e m p e r a t u r e s greater than the 27. W. S. Owen: d. iron Steel Inst., 1957, vol. 177, p. 445.
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ductile/brittle transition temperature, fracture in the
Materials, 1963.
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The research was conducted under the auspices of 33. R. M. Horn and R. O. Ritchie: Proc. 106thAnnualAIMEMeeting, Atlanta,
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34. F. J. Witt: Practical Application of Fracture Mechanics to Pressure-Vessel
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METALLURGICAL TRANSACTIONS A VOLUME 9A, AUGUST 1 9 7 8 - 1 0 5 3