Documenti di Didattica
Documenti di Professioni
Documenti di Cultura
AND
ROBERT
O. RITCHIE
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
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
ISSN 0360-2133/78/0810-1039500.75/0
9 1978AMERICANSOCIETYFOR METALSAND
THE METALLURGICALSOCIETYOF AIME
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.
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 ) .
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
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 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
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 ,
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 austenitization,32,47 rather than during tempering,as is generallythe case for temperembrittlement.
this instance P and N, to prior austenite grain boundaries promoted by the co-segregation of Mn and possibly Si. Furthermore, attempts were made to rationalize a combined role of impurities and carbide precipitation by suggesting that during the growth of carbides, impurity elements are rejected giving rise to
a local increase in impurity concentration at carbide/
matrix interfaces. More recently, attention has once
more focused on the role of retained austenite on TME
based on new data concerning the distribution, morphology, and thermal and mechanical stability of r e tained austenite during tempering.'3'18,a3 The objective
of the present investigation is to reassess this role
of retained austenite in the light of this new information, and to attempt to elucidate specific mechanisms
EXPERIMENTAL
PROCEDURES
Mn
Cr
Ni
Mo
Si
4340 0.41 0.80 0.79 1.75 0.23 0.26 0.004 0.006 300-M 0.42 0.76 0.76 1.76 0.41 1.59 0.002 0.007 0.10
Cu
0.06
-
3~176
.......... ]
COOLINGPROFILE SCHEMATIC
800
94 ~ -
CCT DIAGRAM
~acr
a:
t i12111
4o(3
200
I0
I0 2
TIME (SEC)
[0 3
IO 4
Fig. 1-Schematic diagram displayingcoolingtreatments investigated on transformation diagram for 300-M steel.
METALLURGICAL TRANSACTIONS A
to 650~
The prior austenite grain s i z e of all s t r u c 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
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
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
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
r e s p e c t to such standards, for all t e s t s except for
Table
I. Heat-Treatments
300--
TENSILEPROPERTIES OF 300-M
ISOTHERMALLY TRANSFORMEDAT 250*C
--
2000
iI~,,,,._9 T.S
250
Investigated
-- 1500
Cooling Treatment
After Austenitization for 1 h at 870~
Steel
It
~
2OO
Designation
Yield
Stress
300-M
300-M
300-M
Oil quenched
Isothermally held for 1 h at 250~
Slow continuously cooled to simulate air-cooling of 50
turn thick plate
Oil quenched
Slow continuously cooled to simulate air cooling of 25
mm thick plate
4340
4340
300-M-QT
300-M-ISO
300-M-AC
4340-QT
4340-AC
150
2OO
4OO
TEMPERING TEMPERATURE (*C)
-- I000
6O0
(c)
350
I
I
I
I
TENSILE PROPERTIES O F 300-M
35C
E Q~~ENc H
~ AISI 43~0
30C
!2000
co 2 5 0
25C
E
- - 1500
1500
2OO
Yield
150
I
I00
200
300
400
500
600
TEMPERING TEMPERATURE (%)
(a)
~00
OOO
I00
3O0
I
\ \
Stress"
150
I000
700
--
I" M
TENSILE PROPERTIES OF
AIR COOLED, 5.OCM THICK
:0OO
I00
200
300
400
500
600
TEMPERING TEMPERATURE (~
700
(d)
2 5 C _e
250
.T.S.
500
h
zoc
A
150
9
9
AVERAGEDVALUES
SINGLETEMPER
DOUBLETEMPER
2.....
L~
tr
DO0
I
1500
200
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
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 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 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 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 . )
150
I000
IOO
METALLURGICAL TRANSACTIONS A
I00
I
0
IO0
200
300
400
500
TEMPERING TEMPERATURE (~
600
700
(e)
VOLUME 9A, AUGUST 1978-1041
OIL QUENCHED
Austenitized I hr at 870~
tempered for I hr
I00
oil quenched,
I00
80
80
hi
50 (~
Z
"r
I--
I---
40
ZO
ZO
0
RESULTS
The heat treatments investigated, namely oil quenching, air cooling, and isothermal holding after austenitization, are illustrated schematically in Fig. 1, and
are listed in Table I. Uniaxial tensile properties at
ambient temperature for the five treatments are shown
in Fig. 2 as a function of tempering temperature. Oil
quenched 300-M (300-M-QT) develops peak strength
after tempering at 300~ (Fig. 2(a)), and is significantly
stronger than the air-cooled (300-M-AC) and isothermally-held (300-M-ISO) structures. Peak strength for
the latter treatments is also attained after tempering
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
quenched structures (4340-QT) being significantly
stronger than air-cooled structures (4340-AC). It is
apparent that the increased silicon content in 300-M
leads to i) higher overall strength levels than in 4340,
due to solid solution strengthening and ii) a change in
the kinetics of tempering27 which shifts the optimum
tempering temperature for peak strength from 200~
in 4340 to 300~ in 300-M*. Although tensile proper-
500-M-
1
too
I
z00
I
300
1
400
I
5OO
I
600
7oo
Fig. 3-Effect of tempering temperature on the room temperature plane strain fracture toughness (K[c) of 300-M steel,
oil quenched.
'
--
500-M
"
ALLOY
Austenitized
STEEL
I hr at 870~
- QUENCHED
I'''
AND TEMPERED
60
4O
50
I
40
m
-.N
;I1
:E
5 0 -<
i20
2O
IO
I0
O
,
I
O
IOO
Asque~ched
1
J
1
i
I
~
l
~
I
200
300
400
500
6OO
TEMPERING TEMPERATURE (~
0
700
Fig. 4-Effect of tempering temperature on the room temperature Charpy V-notch impact energy of 300-M steel, oil
quenched.
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
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 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 .
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
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 1044-VOLUME 9A, AUGUST 1978
Fig. 8-Effect of tempering temperature on the room temperature plane strain fracture toughness of 300-M steel, aircooled (50 mm thick plate).
Fig. 9-Effect of tempering temperature on the room temperature plane strain fracture toughness of 300-M steel, isothermally held at 250~ 1 h.
METALLURGICALTRANSACTIONSA
Fig. l l - T r a n s m i s s i o n electron microscopy of 300-M, aircooled 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
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
the TME trough, which can be s e e n to be p a r t i c u l a r l y
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 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
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
trough, r e s p e c t i v e l y ) , a r e shown in Fig. 16 for the
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
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
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
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 .
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
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
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 )
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
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
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
within a lath m a r t e n s i t i c s t r u c t u r e . 49
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 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
shown in F i g s . 17 and 18 for the 4340-QT and 4340-AC
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
Fig. 12-Variation of percentage of retained austenite, measured by magnetic saturation, with tempering temperature
for 300-M, air-cooled. (Unstressed. 0.2 pct strain, 2 pct
strain levels shown.)
Steeland
Treatment
300-M
Oil quenched
300-M
Isothermally
held at 250~
300-M
50 mm, air
cooled
300-M
100 mm, air
cooled
4340
Oil quenched
4340
25 ram, air
cooled
Tempering
Tempering
Maximum
Regimefor
Regimefor
Toughness
Austenite Austenite
Embrittlement Drop,MPa-v/-m Destabilization Level,Pet
~400oc
>~400~
~425~
30
~>400~
12
~450~
40
~>425~
14
~450~
70
~>425~
25
..~275OC
~>250~
~275~
~>275~
METALLURGICAL TRANSACTIONS A
DISCUSSION
'
12C
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
currently held views on tempered martensite embrittlement are that the embrittlement is associated with
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
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
20
AT 250~
Austenitized Ihr at 870~
held at 250~ Ihr, oil cooled, _
tempered
for Ihr
Prior to loading
- - . e - - At yield (e =0.002)
- - - o---At 2 % strain ( e = 0,0 2)
18
16
==
'
pit cooled,
IO0
I0(3
8O
:E
8C
(~
o3
hi
~ 6c
F-
o 14
W
IX
I--
J2
4O
~ 40
(,') I0
/
/
//
r'~
,,, 8 _z
//
I---
"' 6 --
/
/ /
_
/"
/"
p,
"\
/"
"\.
/"
200
\'\
/"
-d
K)O
200
300
400
500
600
TEMPERIN G TEMPERATURE (~
~ lOC
--
80
~.
I00
200
500
400
500
TEMPERING TEMPERATURE r
600
40
700
2O
lOG
200
:300
400
500
600
TEMPERING TEMPERATURE (~
700
I
I
I
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 ent study that, depending on the t h e r m a l and m e c h a n i 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
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 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
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
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
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 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 tion. Changing the s i l i c o n content of the s t e e l , which
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
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
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 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
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 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
trough (300~ t e m p e r ) to a m e r e 40 MPa~r-m at the
' b o t t o m ' (450~ t e m p e r ) . The o n s e t of this 70 MPa~rm
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 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 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
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
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
Tempering
Treatment
300~
400~
470~
Austenite,Pet
ao(311)3'
ao(220)3'
13.2
14.6
3.2
3.627A
3.611A
3.598A
3.628A
3.616A
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
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
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
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
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
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,
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 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
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
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
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 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,
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
grain boundary
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
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
austenite grain boundaries
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
.
ing austenitization
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
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
Fig. 22-Schematic diagrams of mechanisms of tempered
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
martensite embrittlement showing resultant fracture modes
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 prec 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
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
grain boundaries. Cases (a), (b) or (c) tested at a temperal 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
ture above the ductile to brittle transition temperature may
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
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 4340type 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 mechanical 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 improve resistance to very low growth rate, near-threshold, fatigue crack propagation
when compared at equivalent cyclic strength. 46
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 consequence 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
austenite, the combination of cementite precipitates
and mechanically
unstable austenite on lath boundaries
leads to fracture by interlath cleavage in the embritt 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 .
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
or are particularly
s u s c e p t i b l e to i m p u r i t y - i n d u c e d
embrittlement,
the combination of cementite precipitates and residual impurity elements on prior anst 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 ular cracking in the embrittlement
range.
4) In steels containing small levels of austenite and
impurities,
the tensile cracking of brittle cementite
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
fracture by transgranular
cleavage in the embrittlement range.
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
ductile/brittle
transition temperature,
fracture in the
embrittlement
range may additionally involve ductile
rupture.
AC KNOWLEDGE
ME N TS
The research
was conducted under the auspices of
the U.S. Energy Research
and Development
Administration through the Materials
and Molecular Research
Division of the Lawrence Berkeley Laboratory~
The
a u t h o r s w i s h to t h a n k P r o f e s s o r s
E~ R . P a r k e r a n d
V~ F . Z a c k a y f o r t h e i r c o n s t a n t h e l p , s u p p o r t , a n d
encouragement,
a n d M r . J . R . D i l l i o n a n d D r . M . S.
Bhat for experimental
assistance.
Many long, and often
heated, discussions
with Professors
Cohen, McMahon,
Owen, Thomas, Parker,
Zackay, and Drs~ Banerji,
Bhat, Briant, Knott, and Rao on the nature of this topic
are also warmly acknowleged.
REFERENCES
1. J. R. Low, Jr,: in Fract. Eng Mater., ASM, 1964, p. 127.
2. C. I. McMahon, Jr.: ASTM STP 407, p. 127, American Society for Testing
and Materials, 1968.
3. E. B. Kula and A. A. Anctil: J. Mater., 1964, voL 4, p. 817.
4. B. J. Schulz and C. J. McMahon, Jr.: ASTM STP 499, p. 104, American
Society for Testing and Materials, 1972.
5. M. A. Grossmann: Trans. AIME, 1946, vol. 167, p. 39.
6. H. Schrader, It. J. Wiester, and H. Siepmann: Arch. Eisenhuettenw., 1950,
vol. 21, p. 21.
7. R. L. Pickett and J. M. Hodge: Proc. ASTM, 1951, vol. 51, p. 931.
8. L. J. Klingler, W. J, Barnett, R. P. Frohmberg, and A. R. Troiano: Trans. ASM,
1954, vol. 46, p. 1557.
9. J. J. hani, M. J. May, and D. Eltiott: ASTM STP 407, p. 168, American Society
for Testing and Materials, 1968.
10. E. J. Ripling: Trans. ASM, 1950, vol. 42, p. 439.
11. G. V. Luerssen and O. V. Greene: Ibid, 1935, vol. 23, p. 861.
12. L. S. Castleman, B, L. Averbach, and M. Cohen: 1bid, 1952, vol. 44, p. 240.
METALLURGICAL TRANSACTIONS A