Effect of Cooling Rate and Alloying on the

Transformation of Austenite

B. L. BRAMFITT AND A. R. MARDER

The p e a r l i t i c h a r d e n a b i l i t y of a h i g h - p u r i t y F e - 0 . 8 p c t C a l l o y and z o n e - r e f i n e d i r o n b i n a r y
a l l o y s c o n t a i n i n g Mn, Ni, Si, Mo, o r Co was s t u d i e d b y m e a n s of h o t - s t a g e m i c r o s c o p y . The
b i n a r y a l l o y s w e r e c a r b u r i z e d in a g r a d i e n t f u r n a c e to p r o d u c e e u t e c t o i d c o m p o s i t i o n s , thus
e l i m i n a t i n g p r o e u t e c t o i d p h a s e s . A s p e c i a l technique b a s e d on h o t - s t a g e m i c r o s c o p y was
u s e d to s t u d y the effect of c o o l i n g r a t e ( 1 0 ~ to 25,000~ on the t r a n s f o r m a t i o n of
a u s t e n i t e and p r o v i d e d d a t a for the c o n s t r u c t i o n of continuous c o o l i n g - t r a n s f o r m a t i o n d i a -
g r a m s . F r o m t h e s e d i a g r a m s c r i t i c a l c o o l i n g r a t e s w e r e o b t a i n e d for h a r d e n a b i l i t y c a l c u -
l a t i o n s . It was found that m o l y b d e n u m is the m o s t e f f e c t i v e e l e m e n t , followed b y Si, Ni. Co,
and Mn, in s u p p r e s s i n g the p e a r l i t e t r a n s f o r m a t i o n , i.e., in i n c r e a s i n g the h a r d e n a b i l i t y of
the a l l o y s s t u d i e d . The a l l o y i n g a d d i t i o n s w e r e g r o u p e d into two c l a s s e s a c c o r d i n g to t h e i r
effect on h a r d e n a b i l i t y : a - s t a b i l i z e r s (Mo and Si) and v - s t a b i l i z e r s (Ni, Co, Mn), with the
a - s t a b i l i z e r s b e i n g the m o r e e f f e c t i v e in i m p r o v i n g h a r d e n a b i l i t y .

LONG a w a r e of the c o m m e r c i a l i m p o r t a n c e of h a r d e n - In the p r e s e n t w o r k we s t u d i e d the effect of c o n t i n u -

a b i l i t y , m e t a l l u r g i s t s have o v e r the y e a r s been s t u d y - ous cooling on the t r a n s f o r m a t i o n of b i n a r y i r o n - c a r -
ing the c o m p o s i t i o n a l and m i c r o s t r u c t u r a l f a c t o r s a f - bon a s well a s a n u m b e r of high p u r i t y t e r n a r y a l l o y s .
f e c t i n g h a r d e n a b i l i t y in o r d e r to d e v e l o p a l l o y d e s i g n The d a t a thus o b t a i n e d w e r e then u s e d to c l a s s i f y the
c r i t e r i a , p a r t i c u l a r l y for m o d e r n h i g h - s t r e n g t h a p p l i - k i n e t i c b e h a v i o r of a l l o y i n g e l e m e n t s a s v - f o r m e r s o r
c a t i o n s . F o r e x a m p l e , p a r t l y b e c a u s e of the s t i m u l u s a-formers.
of the p r o p e r t y r e q u i r e m e n t s f o r new s t e e l s f o r s h i p s , Two t e c h n i q u e s w e r e d e v e l o p e d for this s t u d y : a) a
a i r c r a f t , and o r d n a n c e in the e a r l y 1940's, G r o s s m a n , 1 g r a d i e n t f u r n a c e technique for p r o d u c i n g a l l o y s of e u -
followed b y o t h e r s , 2-4 d e v e l o p e d s o m e of the b a s i c quan- t e c t o i d c o m p o s i t i o n , and b) a p r o c e d u r e using the h o t -
t i t a t i v e d a t a for such a l l o y d e s i g n n e e d s . T h e i r w o r k s t a g e m i c r o s c o p e , b y which we s t u d i e d and r e c o r d e d
a l l o w e d m e t a l l u r g i s t s to a p p r o x i m a t e the " i d e a l c r i t i - the t h e r m a l e v e n t s and a s s o c i a t e d m i c r o s t r u c t u r a l
c a l d i a m e t e r " of a s t e e l b a r by using m u l t i p l y i n g f a c - c h a n g e s in a l l o y s d u r i n g cooling and t r a n s f o r m a t i o n .
t o r s for c h e m i c a l c o m p o s i t i o n and g r a i n s i z e . Many Throughout the study, c i n e p h o t o m i c r o g r a p h y was u s e d
s t e e l s w e r e s u b s e q u e n t l y d e s i g n e d using t h i s b a s i c d a t a to a c c u r a t e l y r e c o r d the m i c r o s t r u c t u r a l c h a n g e s . F o r
f o r h a r d e n a b t l i t y c a l c u l a t i o n s , d a t a which is s t i l l in the p r e s e n t s t u d y only the extent of p e a r l i t i c t r a n s f o r -
wide use today. m a t i o n a s a m e a s u r e of h a r d e n a b i l i t y has b e e n c o n s i d -
F u n d a m e n t a l to the p r o b l e m s of d e s i g n i n g a l l o y s for e r e d . The h o t - s t a g e technique o f f e r e d a f a s t m e t h o d
o p t i m u m h a r d e n a b i l i t y f o r s p e c i f i c a p p l i c a t i o n s is a of s t u d y i n g i n d i v i d u a l a l l o y i n g e f f e c t s on t h i s t r a n s f o r -
sound knowledge of the m e c h a n i s m s of a l l o y i n g b e h a v - m a t i o n p r o d u c t , thus y i e l d i n g s i g n i f i c a n t i n f o r m a t i o n
i o r and the c o m p l e x r o l e of m u l t i p l e c o m b i n a t i o n s of on h a r d e n a b i l i t y .
a l l o y i n g e l e m e n t s in t h e s e m e c h a n i s m s . In c o n t r a d i s -
t i n c t i o n to G r o s s m a n , 1 who p o s t u l a t e s m u l t i p l i c a t i v e
a l l o y e f f e c t s on hardenability,per se, Hollomon and EXPERIMENTAL PROCEDURE
Jaffe c o n s i d e r e d the effect of a l l o y i n g on " p e a r l i t i c and The s t a r t i n g m a t e r i a l s for the h a r d e n a b i l i t y s t u d i e s
b a i n i t i c h a r d e n a b i l i t y , " i.e., the a b i l i t y to a v o i d the w e r e z o n e - r e f i n e d i r o n b i n a r y a l l o y s containing Mo,
pearlite. Ni, Co, Mn, and Si (Table I). Rods of t h e s e a l l o y s , 88in.
Another s o u r c e of i n f o r m a t i o n in this a r e a was p r o - in d i a m , w e r e c o l d - r o l l e d into 2 0 - m i l s h e e t for f u r t h e r
v i d e d b y the i s o t h e r m a l - t r a n s f o r m a t i o n (I-T) d i a g r a m s processing.
r e s u l t i n g f r o m a s e r i e s of i s o t h e r m a l h e a t t r e a t m e n t To p r o d u c e h i g h - p u r i t y b i n a r y and t e r n a r y e u t e c t o i d
s t u d i e s . 5 T h e s e d i a g r a m s a r e useful in p r e d i c t i n g the a l l o y s we u s e d a s p e c i a l g r a d i e n t f u r n a c e technique ~
microstructural changes during isothermal transfor- c o n s i s t i n g of the d y n a m i c c a r b u r i z a t i o n of the s h e e t
m a t i o n . Other i n v e s t i g a t i o n s 6-8 r e s u l t e d in a s e r i e s of m a t e r i a l in a g a s e o u s m i x t u r e of m e t h a n e and h y d r o g e n
continuous c o o l i n g - t r a n s f o r m a t i o n ( C - T ) d i a g r a m s that (1:20 r a t i o ) at a t e m p e r a t u r e of 1800~ Each s p e c i -
p r o v i d e guidance to the a l l o y d e s i g n e r b y p r e d i c t i n g m e n d u r i n g c a r b u r i z a t i o n was p a s s e d through a s t e e p
the p h a s e s that r e s u l t upon continuous cooling c o n d i - t e m p e r a t u r e g r a d i e n t of 3500~ at a r a t e of 2.8
t i o n s , e.g., oil quenching. • 10 -s i n . / s , and the s p e c i m e n o b t a i n e d was e n t i r e l y
p e a r l i t i c , i.e., f r e e f r o m p r o e u t e c t o i d p h a s e s . The c a r -
B. L. BRAMFITT and A. R. MARDER are Engineer and Supervisor, bon contents of the t e r n a r y a l l o y s a f t e r c a r b u r i z a t i o n
respectively, Transformations and Strengthening Mechanisms Group,
w e r e h i g h e r (about 1 p c t C) than t h o s e Bain and Paxton
Alloy Development Section, Research Department, Bethlehem Steel
Corporation, Bethlehem, Pa. 18016. This paper is based on a presenta- r e p o r t e d f o r the t e r n a r y e u t e c t o i d s w h e r e the addition
hon made at a symposium on "Hardenability" held at the Cleveland of a t h i r d a l l o y i n g e l e m e n t l o w e r s the c a r b o n l e v e l to
Meeting of The Metallurgical Society of AIME, October 17, 1972, b e l o w 0.8 p c t C. I~ The c a r b o n content for the F e - C
under the sponsorship of the IMD Heat Treatment Committee. b i n a r y a l l o y was c o n s i s t e n t with the F e - C p h a s e d i a -

METALLURGICAL TRANSACTIONS VOLUME 4, OCTOBER 1973-2291

 corded at the s a m e t i m e as one r e c o r d s t h e r m a l h i s -
Table I. Chemical Analysis of Alloys t o r y data such as t h e r m a l a r r e s t s , cooling r a t e s and
heating r a t e s . A p l a t i n u m / p l a t i n u m - 1 0 pct r h o d i u m
C Mn $1 N1 Co Mo
t h e r m o c o u p l e was s p o t - w e l d e d to each s p e c i m e n u s i n g
Binary Alloy 0.80 <0.01 <0.01 0.02 <0.002 the s p e c i m e n as the hot ]unction, a t h e r m o c o u p l e bead
low-mckel alloy 1.05" T T 0.46 ND T being u n d e s i r a b l e b e c a u s e of the i n h o m o g e n e o u s t e m -
high-mckel alloy 0.94* T T 3.35 ND T p e r a t u r e g r a d i e n t s d u r i n g cooling r a t e s t u d i e s . All
low-cobalt alloy 0.94* ND ND 0.01 0.49 T heating and cooling t r e a t m e n t s w e r e p e r f o r m e d u n d e r
high-cobalt alloy 1.30" ND T 0.02 1.00 T a high-purity argon atmosphere.
low-manganese alloy t.00" 0.43 ND T ND T The s p e c i m e n s were placed in the f u r n a c e and heated
high-manganese alloy 1.00" 0.78 ND T ND T to 1850~ for 2 m i n and then cooled at a c o n t r o l l e d r a t e
low-molybdenum alloy 1.00" ND ND ND ND 0.23 to r o o m t e m p e r a t u r e . Cooling r a t e s r a n g i n g f r o m 1 0 ~
high-molybdenum alloy 1.06" ND 0.005 0.001 ND 0.45 m i n to 2 5 , 0 0 0 ~ were used for the e x p e r i m e n t s .
low-stilton alloy 1 00" ND 0.30 T ND T
The fast cooling r a t e s were obtained by quenching the
s p e c i m e n with h e l i u m gas cooled to a t e m p e r a t u r e of
*Carbon analysis obtained after carburlzation in gradient furnace. - 125~ The slower cooling r a t e s were obtained by
T-Trace, ND None Detected
c o n t r o l l i n g the f u r n a c e c u r r e n t by m e a n s of a m o t o r -
ized v a r i a b l e r h e o s t a t . All h e a t - t r e a t i n g c y c l e s w e r e
g r a m . We t h e r e f o r e t e s t e d the c a r b u r i z e d s p e c i m e n s r e c o r d e d on a c a l i b r a t e d s t r i p - c h a r t r e c o r d e r , and the
by r e a u s t e n i t i z i n g them in a s t a n d a r d f u r n a c e and a l - actual cooling r a t e and t h e r m a l a r r e s t t e m p e r a t u r e s
lowing them to f u r n a c e - c o o l to find out whether the were taken f r o m the cooling c u r v e .
g r a d i e n t t r e a t m e n t p r o d u c e d an e q u i l i b r i u m p e a r l i t i c During the cooling p r o c e s s the growth of p e a r l i t e
s t r u c t u r e u n d e r n o n g r a d i e n t c o n d i t i o n s ; in no case w e r e a n d / o r m a r t e n s i t e was o b s e r v e d in the m i c r o s c o p e
p r o e u t e c t o i d p h a s e s p r e s e n t in the b i n a r y or t e r n a r y using p h a s e - c o n t r a s t o b j e c t i v e s . The growth of p e a r l -
alloys under i n v e s t i g a t i o n . ite f r o m a u s t e n i t e was b a r e l y d i s c e r n i b l e when c o m -
P r o d u c i n g an e q u i l i b r i u m eutectoid c o m p o s i t i o n by p a r e d with the f o r m a t i o n of m a r t e n s i t e , which is e a s i l y
m e a n s of the g r a d i e n t technique is b a s e d on s a t u r a t i o n o b s e r v e d due to the s u r f a c e upheaval c r e a t e d upon cool-
of the a u s t e n i t e with c a r b o n . At the a u s t e n i t i z a t i o n t e m - ing. After each t h e r m a l cycle, the s p e c i m e n was r e -
p e r a t u r e of 1800~ the a m o u n t of c a r b o n r e q u i r e d for moved f r o m the h o t - s t a g e and e x a m i n e d m e t a l l o g r a p h -
c o m p l e t e s a t u r a t i o n in the b i n a r y F e - C alloy s y s t e m i c a l l y to make c e r t a i n that the m i c r o s t r u c t u r e was con-
was about 1.5 pct. As each s p e c i m e n p a s s e d through s i s t e n t throughout the s p e c i m e n and not m e r e l y a s u r -
the steep t e m p e r a t u r e g r a d i e n t , it r a n g e d in t e m p e r a - face p h e n o m e n o n .
t u r e f r o m 1800~ at one end to r o o m t e m p e r a t u r e at The growth r a t e of the t r a n s f o r m i n g phase can be a c -
the other end and the c a r b o n c o n c e n t r a t i o n of the a u - c u r a t e l y m e a s u r e d f r o m the c i n e p h o t o m i c r o g r a p h s . The
s t e n i t e d e c r e a s e d f r o m the s a t u r a t e d amount down to technique allows one to m e a s u r e the growth r a t e in any
that of the eutectoid c o n c e n t r a t i o n at the eutectoid t e m - d i r e c t i o n f r o m the n u c l e a t i o n site as well as the growth
p e r a t u r e . As a m a t t e r of fact, in the i r o n - c a r b o n b i n a r y r a t e of s i m u l t a n e o u s e v e n t s in the s p e c i m e n . A c c u r a t e
phase d i a g r a m this c o n c e n t r a t i o n of c a r b o n in the a u - m e a s u r e m e n t s can also be made d u r i n g the i m p i n g e -
s t e n i t e follows a path along the Acm line. Consequently, m e n t of two or m o r e t r a n s f o r m a t i o n p r o d u c t s .
by the t i m e the eutectoid t e m p e r a t u r e has b e e n r e a c h e d ,
the a u s t e n i t e of eutectoid c o m p o s i t i o n has t r a n s f o r m e d
c o m p l e t e l y to p e a r l i t e . Of c o u r s e , in t e r n a r y s y s t e m s RESULTS AND DISCUSSIONS
the s i t u a t i o n is m o r e c o m p l i c a t e d ; however, Yue, n u s - Our r e s u l t s a r e d i s c u s s e d under t h r e e m a i n h e a d i n g s :
ing a technique s i m i l a r to our g r a d i e n t f u r n a c e t e c h - 1) r e s u l t s of our h o t - s t a g e m i c r o s c o p i c study of the
nique, i.e., z o n e - r e f i n i n g , has e s t a b l i s h e d a c c u r a t e e u - t r a n s f o r m a t i o n of a u s t e n i t e , 2) the effect of cooling
t e c t i c c o m p o s i t i o n s for c o m p l e x alloy s y s t e m s c o n s i s t - r a t e on the F e - C b i n a r y alloy, and 3) the effect of cool-
ing of four and six d i f f e r e n t e l e m e n t s . ing r a t e on F e - C t e r n a r y a l l o y s .
The m a i n advantage of our g r a d i e n t f u r n a c e technique
is that a eutectoid s t r u c t u r e is e a s i l y obtained, w h e r e a s
Hot-Stage M i c r o s c o p y of the T r a n s f o r m a t i o n
it m a y take s e v e r a l alloys and detailed c h e m i c a l and
of Austenite
m e t a l l o g r a p h i c a n a l y s i s to obtain the s a m e s t r u c t u r e
u s i n g m e l t i n g and c a s t i n g t e c h n i q u e s , where the addi- The v i s u a l r e s u l t s of any h o t - s t a g e technique depend
t i o n a l f a c t o r of s e g r e g a t i o n o c c u r s d u r i n g s o l i d i f i c a t i o n . on s u r f a c e r e l i e f of the t r a n s f o r m a t i o n p r o d u c t which
C a r b o n s e g r e g a t i o n e x i s t s in the g r a d i e n t f u r n a c e s p e c - p r o d u c e s a c o n t r a s t effect that can be o b s e r v e d d u r i n g
i m e n but only in the final p o r t i o n of the s p e c i m e n that t r a n s f o r m a t i o n . T h e r e have b e e n s e v e r a l p r e v i o u s hot-
t r a n s f o r m s l a s t . This h i g h - c a r b o n r e g i o n can e a s i l y stage light m i c r o s c o p y s t u d i e s to o b s e r v e the f o r m a t i o n
be r e m o v e d and d i s c a r d e d . of m a r t e n s i t e 13 and b a i n i t e . 14-16 These two t r a n s f o r m a -
The c a r b u r i z e d s p e c i m e n s w e r e cut into ~ - i n . tions involve a c o n s i d e r a b l e a m o u n t of s u r f a c e upheaval
s q u a r e s for the h o t - s t a g e m i c r o s c o p e , a d e s c r i p t i o n of due to a s h e a r m e c h a n i s m . The f o r m a t i o n of p e a r l i t e ,
which has been p u b l i s h e d . 12 The h o t - s t a g e m i c r o s c o p e however, has r e c e i v e d little a t t e n t i o n in the l i t e r a t u r e ,
was modified for this i n v e s t i g a t i o n to include a c a p a - p r o b a b l y b e c a u s e it is not e a s i l y detected b y light op-
b i l i t y for the t h e r m a l a n a l y s i s of phase t r a n s f o r m a t i o n s . t i c s . However, when p h a s e - c o n t r a s t o b j e c t i v e s a r e
With this modification, the h o t - s t a g e m i c r o s c o p e b e - used, the growth of p e a r l i t e f r o m a u s t e n i t e can be s e e n
c o m e s an e x c e l l e n t tool for the study of t r a n s f o r m a - in the h o t - s t a g e m i c r o s c o p e . For e x a m p l e , Fig. 1
t i o n s . While a given t r a n s f o r m a t i o n is being o b s e r v e d , shows the s e q u e n c e of growth of a p e a r l i t e nodule
m i c r o s t r u c t u r a l changes can be p h o t o g r a p h i c a l l y r e - (arrow) at the j u n c t u r e of t h r e e n e i g h b o r i n g a u s t e n i t e

2292-VOLUME4, O C T O B E R 1973 METALLURGICAL TRANSACTIONS

 0.44 0.86 1,44 1.78

2.24 2 62 2.88 3.09 sec.

Fig. 1--Cinephotomicrographic sequence of growth of a pearlite nodule (arrow) at the junction of three austenite grains ; cooling
rate 4800~ and transformation temperature 1090~ Magnification ~bout 250 times.

g r a i n s . The c o o l i n g r a t e in t h i s p a r t i c u l a r e x a m p l e was p o r t a n t to keep this in mind when c o n s i d e r i n g g r o w t h -

4800~ with the t r a n s f o r m a t i o n t a k i n g p l a c e at r a t e m e a s u r e m e n t s on the s u r f a c e . When, h o w e v e r ,
1090~ If the growth p r o c e s s w e r e i n t e r r u p t e d by a f a s t the nodule is s e c t i o n e d , its c e n t e r can be l o c a t e d and
quench with c o l d h e l i u m g a s , the u n t r a n s f o r m e d a u s t e n - c o r r e c t i o n s in g r o w t h can be m a d e using s i m p l e g e o -
ite would t r a n s f o r m to m a r t e n s i t e at the M s t e m p e r a - metric relationships.
t u r e . An e x a m p l e of this technique is shown in Fig. 2. Although s o m e w h a t o u t s i d e the s c o p e of the p r e s e n t
The a c t u a l s u r f a c e r e l i e f (Fig. 2(a)) is shown along with study, an e x a m p l e of the m e a s u r e m e n t of growth r a t e
the e t c h e d p e a r l i t e r e g i o n (Fig. 2(b)). The p e a r l i t e nod- is given. A c i n e p h o t o m i c r o g r a p h i c s e r i e s of the s t a g e s
u l e s c o n s i s t of m a n y p e a r l i t e c o l o n i e s of d i f f e r i n g o r i - of growth of a p e a r l i t e nodule is shown in Fig. 4(a),
entation, and the nodules g e n e r a l l y n u c l e a t e at a u s t e n - which r e p r e s e n t s a cooling r a t e of 5 3 0 0 ~ and a
ite g r a i n b o u n d a r i e s and grow in a s p h e r i c a l g e o m e t r y t r a n s f o r m a t i o n t e m p e r a t u r e of 1090~ The growth
until t h e y i m p i n g e on o t h e r nodules. In this c a s e , the r a t e of 56 /~m/s shown in Fig. 4(b) was m e a s u r e d f r o m
f o r m a t i o n of p l a t e m a r t e n s i t e p r e v e n t e d i m p i n g e m e n t . the nodule shown in Fig. 4(a) ( a r r o w ) . The growth r a t e
Throughout the i n v e s t i g a t i o n , s p e c i m e n s w e r e p o l - for the o t h e r nodule g r o w i n g at the j u n c t u r e of the t h r e e
i s h e d and e t c h e d in c r o s s s e c t i o n to m a k e c e r t a i n that a u s t e n i t e g r a i n s is s o m e w h a t l o w e r at 49 p m / s . T h e s e
the phenomenon o b s e r v e d on the s u r f a c e had a l s o t a k e n growth r a t e s a r e in good a g r e e m e n t with the d a t a of
p l a c e in the i n t e r i o r of the s p e c i m e n . Fig. 3 shows a F r y e e t a l . , 17 who r e p o r t e d an e x p e r i m e n t a l v a l u e of
t y p i c a l c r o s s - s e c t i o n view at m a g n i f i c a t i o n 200 and 500 52.5 ~ m / s for a h i g h - p u r i t y 0.78 pct C s t e e l at a t r a n s -
t i m e s of two d i f f e r e n t s p e c i m e n s that w e r e r a p i d l y f o r m a t i o n t e m p e r a t u r e of 1094~ and with the d a t a of
quenched at a s t a g e in the t r a n s f o r m a t i o n to p e a r l i t e Hull e t a l . , Is who r e p o r t e d a m e a s u r e d v a l u e of 6 5 / ~ m / s
when nodule growth was o c c u r r i n g . As can be s e e n , the f o r a h i g h - p u r i t y 0.93 p c t C s t e e l at l l l 0 ~ Their
nodules n u c l e a t e and grow throughout the s p e c i m e n growth r a t e s w e r e o b t a i n e d by m e a n s of the t e d i o u s
t h i c k n e s s . It is i m p o r t a n t to note, h o w e v e r , that the s a l t - b a t h method, in which the s p e c i m e n s a r e a l l o w e d
s p h e r i c a l growth at the s p e c i m e n s u r f a c e s e e n in the to i s o t h e r m a l l y t r a n s f o r m for v a r i o u s p e r i o d s of t i m e
m i c r o s c o p e is not n e c e s s a r i l y t a k i n g p l a c e at the nod- and a r e then quenched to r o o m t e m p e r a t u r e . The m i -
ule e q u a t o r . In o t h e r w o r d s , the s u r f a c e growth m a y c r o s t r u c t u r e s a r e then e x a m i n e d for the l a r g e s t d i a m -
r e p r e s e n t only a p o r t i o n of the nodule, the c e n t e r of e t e r nodule. The a d v a n t a g e of the h o t - s t a g e technique
which is s u b m e r g e d below the s u r f a c e p l a n e . It is i m - is that the m e a s u r e m e n t s can be m a d e on a s i n g l e s p e c -

METALLURGICAL TRANSACTIONS VOLUME 4, OCTOBER 1973-2293

 Surface 370X

Surface

Surface 150X

Fig. 3--Cross-section views of the microstructure of pearlite

nodules in partially transformed hot-stage specimens, show-
ing nodule forming both at specimen surface and interior.
B Picral.
Fig. 2--Partially transformed and quenched specimen showing: e r a l l y e x p r e s s e d in t e r m s of the "undercooling," AT,
(a) surface relief of specimen in hot-stage (unetehed), and (b) which is s i m p l y the d i f f e r e n c e b e t w e e n the e q u i l i b r i u m
polished and etched (pmral) region below surface. Magnifica-
tion 190 times. and actual t r a n s f o r m a t i o n t e m p e r a t u r e . The u n d e r c o o l -
ing i n c r e a s e s with i n c r e a s i n g cooling r a t e until the
i m e n in which the growth r a t e s of v a r i o u s nodules can c r i t i c a l cooling r a t e is r e a c h e d .
be m e a s u r e d s i m u l t a n e o u s l y . An i n t e r e s t i n g a s p e c t of A c o m p a r i s o n of our continuous cooling data with the
the growth r a t e c u r v e in Fig. 4(b) is that this r a t e , i s o t h e r m a l data of Brown and Ridley 2~ on an alloy of
which a p p a r e n t l y f l u c t u a t e s with t i m e , does not change a l m o s t identical c o m p o s i t i o n is shown in Fig. 6. As
on i m p i n g e m e n t . A s s u m i n g that a " s o f t i m p i n g e m e n t " can be s e e n f r o m Fig. 6, i n c r e a s i n g the cooling r a t e
should take place, Cahn and Hage119 had t h e o r i z e d that s i g n i f i c a n t l y d e p r e s s e s the p e a r l i t e t r a n s f o r m a t i o n
the r a t e would d e c r e a s e at this point. s t a r t . Although this effect is also s e e n in the case of
Brown and R i d l e y ' s data. the d i f f e r e n c e is even m o r e
m a g n i f i e d in t h e i r case by the e l a p s e d t i m e n e c e s s a r y
The Effect of Cooling Rate on the F e - C
for t r a n s f e r of s p e c i m e n s to an i s o t h e r m a l bath. Al-
B i n a r y Alloy
though they do not d i s c u s s t h e i r t r a n s f e r t i m e f r o m the
Specimens of the h i g h - p u r i t y , i r o n - c a r b o n b i n a r y a l - a u s t e n i t i z i n g t e m p e r a t u r e to the i s o t h e r m a l bath, we
loy w e r e s u b j e c t e d to cooling r a t e s r a n g i n g f r o m 12 to e n c o u n t e r e d t r a n s f e r t i m e s of up to two s e c o n d s in
25,000~ The effect of cooling r a t e on the p e a r l - some of our own i s o t h e r m a l s t u d i e s ; thus, if t r a n s f e r
ite t r a n s f o r m a t i o n t e m p e r a t u r e is shown in Fig. 5. A t i m e were taken into account, t h e i r i s o t h e r m a l t r a n s -
l i m i t i n g cooling r a t e , i.e., the c r i t i c a l cooling r a t e for f o r m a t i o n s t a r t c u r v e for p e a r l i t e would be moved to
this alloy, was r e a c h e d at 2 5 , 0 0 0 ~ at which point the right. Hence, on the b a s i s of both types of data r e p -
a m i x t u r e of both m a r t e n s i t e and p e a r l i t e f o r m e d . The r e s e n t e d in Fig. 6, continuous cooling s i g n i f i c a n t l y low-
c r i t i c a l cooling r a t e for this study is defined as the e r s the p e a r l i t e s t a r t t e m p e r a t u r e s and moves the
cooling r a t e at which a s u b s t a n t i a l a m o u n t of m a r t e n - t r a n s f o r m a t i o n to longer t i m e , thus i n c r e a s i n g h a r d e n -
site b e c o m e s o b s e r v a b l e in the light m i c r o s c o p e . The ability. An e x a m p l e of the p e a r l i t i c s t r u c t u r e s found
s u p p r e s s i o n of the t r a n s f o r m a t i o n t e m p e r a t u r e is g e n - at v a r i o u s cooling r a t e s is shown in Fig. 7. The l e t t e r s

2294-VOLUME 4, OCTOBER 1973 METALLURGICALTRANSACTIONS

(.) 0.13 0.37 0.75

(b)
"1
so I
GROWTH OF N O D U L E A(FJ6 4 o )
MAGNIFICATION = 3 4 5 x
FfLMED AT 2'~ F R A M E S / S E C ~"
g"
/

ro

~
/
/
~ RATE = 5 6 IJ4n/lec

o,f~
/
02 04 06 08 I0 12 14 16
TIME,seconds

1.08 1.42 sec.

F i g . 4--(a) C i n e p h o t o m i c r o g r a p h i c s e q u e n c e of a g r o w i n g p e a r l i t e nodule ( a r r o w ) , c o o l i n g r a t e 5300~ p e r m i n and
t r a n s f o r m a t i o n t e m p e r a t u r e 1090~ (b) T h e g r o w t h r a t e c u r v e f o r t h e n o d u l e m (a). M a g n i f i c a t i o n about 350 t i m e s .

~450| , I r Ilr~l I r , , ~llr, I I I II,lll I I I r Ill,

1400 I I-i i1,111 I I r Illll I ~ , i Illl
1400
,350 . . . . . ..................................
_A_~,_
1350 . . . . . . . . . . . . . . A=eL . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
LSO0
/ / ~
1250 / ~ - ~ E R M A L DATA (REF2O)
~ lE50 , " ,
~1200

N,iso
~ 1100
9 CONTINUOUS COOLING DATA
~ 105D
~1000
~ lOOC
95C

900 i
85C I f I mill I I I I mill r I J i Jrdl
I0 I00 tO00
TIME, ur
----l ....... :; ....... ~ ....... I~ . . . . . l()O0o0
COOLING RATE , ~ F/rain
Fig. 6--A comparison of continuous cooling transformation
Fig. 5 - - T h e e f f e c t of c o o l i n g r a t e on t h e p e a r l i t e t r a n s f o r m a - data for the Fe-0.8 pct C alloy with the isothermal transfor-
tion t e m p e r a t u r e for the i r o n - 0 . 8 p c t c a r b o n alloy. mation data of Brown and R1dley for a similar alloy.

METALLURGICAL TRANSACTIONS VOLUME 4, OCTOBER 1973 2295

 A B

C D
Fig. 7--A series of photomicrographs representing the structures produced at eight different cooling rates for the Fe-0.8 pct
alloy. The letters correspond to the lettered data points in Fig. 6. Picral. Magnification 200 times~

c o r r e s p o n d to the l e t t e r e d data points in Fig. 6. It is m a r t e n s i t e f o r m s and s u r r o u n d s the a l r e a d y g r o w i n g

s e e n that as the c o o l i n g r a t e i n c r e a s e s o r t i m e f o r p e a r l i t e nodules.
t r a n s f o r m a t i o n d e c r e a s e s , the p e a r l i t e s t r u c t u r e r e p - The d e v e l o p m e n t and growth of nodules in the c r i t i c a l
r e s e n t e d by the nodules b e c o m e s s m a l l e r . At G and H cooling r a n g e can be s e e n in Fig. 8, w h e r e s e v e r a l

2296-VOLUME 4, OCTOBER 1973 METALLURGICALTRANSACTIONS

 G H
Fig. 7 - - C o n t i n u e d

s m a l l p e a r l i t e nodules grew to the limiting s i z e dictated in Fig. 8 r e p r e s e n t the l i m i t of growth of the p e a r l i t e

by the r e s i d e n c e time at the nose of the C - T d i a g r a m . nodules (arrows) at 0.91 s, the s t a r t of m a r t e n s i t e f o r -
This example has a cooling r a t e between the cooling mation at 3.51 s, continuing formation of m a r t e n s i t e at
r a t e s of G and H in F i g . 6. The c i n e p h o t o m i c r o g r a p h s 3.84 s, and finally the end of t r a n s f o r m a t i o n at 5.71 s.

METALLURGICAL TRANSACTIONS VOLUME 4, OCTOBER 1 9 7 3 - 2 2 9 7

Fig. 8--Cinephotomicrographs representing the critical cooling rate for the Fe-0.8 pct C alloy (near data points G and H in
Fig. 7). Thin series shows the limit of growth of the pearlite nodules (arrow) followed by the formation of martensite.
Magnification about 440 times.

2 2 9 8 - V O L U M E 4, OCTOBER 1973 METALLURGICAL TRANSACTIONS

The d e l a y t i m e f r o m the finish nodule growth to the
b e g i n n i n g of m a r t e n s i t i c growth was 2.60 s. Table II. Comparison of HardenabUity Data

MulUplymg Factor
The Effect of Cooling Rate on F e - C Element Ref. 22, 1967 Ref 21, 1946 Ref. 1, 1942 Ref. 2, 1944
Ternary Alloys
Mo 2.9 2.9 2.4 2.4
The effect of c o o l i n g r a t e on the p e a r l i t e t r a n s f o r - Mn 1.3 1.2 2.5 2.9
m a t i o n t e m p e r a t u r e s of the five t e r n a r y a l l o y s c o n t a i n - Si 1.2 1.3 1.4 1.5
ing Ni, Mn, Co, Mo, o r Si is shown in F i g s . 9(a) t h r o u g h Ni 1.1 1.4 1.2 1.1
Co
(e), r e s p e c t i v e l y . Two c o m p o s i t i o n l e v e l s a r e shown for - - - 1.0

e a c h a l l o y , e x c e p t i n g the s i l i c o n one. The c o o l i n g r a t e s

varied from 71~ to the c r i t i c a l c o o l i n g r a t e ,
which is i n d i c a t e d in each g r a p h . To c o m p a r e the r e l a -
Table III. Hardenability Comparison of Alloying Additions
t i v e e f f e c t s of a l l o y on the C - T d i a g r a m b e h a v i o r , we
i n c l u d e d F i g . 10, which shows the c o m p o s i t e C - T d i a - Alloying Wt Pct Alloy/Pct
g r a m s f o r a c o n s t a n t a l l o y l e v e l of 0.45 wt p c t (except Element Increase M.F. Ref.
for Si at a l e v e l of 0.3 wt pct). In g e n e r a l , it can be
Ti 0.014 to 0.080 3, 25
s e e n t h a t m o l y b d e n u m h a s the g r e a t e s t effect in s u p - V 0 04 to 0.30 1, 3
p r e s s i n g the t r a n s f o r m a t i o n t e m p e r a t u r e , s i l i c o n , Mo 0.16 to 0.20 1, 3
n i c k e l , cobalt, and m a n g a n e s e following in d e s c e n d i n g a-stabilizers Zn 0 20 3
o r d e r . This t r e n d is shown in Fig. 11, w h e r e the s u p - Cr 0.22 to 0.36 3, 22
Al 0.55 3
p r e s s i o n of the t r a n s i t i o n t e m p e r a t u r e is e x p r e s s e d in
$1 0.55 to 0.75 1, 25
t e r m s of p e r c e n t a l l o y at a c o n s t a n t c o o l i n g r a t e (10~
p e r min). The t r e n d for m o l y b d e n u m and s i l i c o n is d i f - Mn 0.60 to 0.80 21,25
3'-stabilizers Ni 1.15 to 1.30 1, 25
f e r e n t f r o m that for nickel, c o b a l t , and m a n g a n e s e . Cu >1.5 25
This d i f f e r e n c e in the two t r e n d s is c o n s i s t e n t f o r the
e n t i r e r a n g e of c o o l i n g r a t e s and i n d i c a t e s that m o l y b -
denum is the m o s t e~fective a l l o y i n g a d d i t i o n for i m -
p r o v i n g h a r d e n a b i l i t y . The d e p e n d e n c y of c r i t i c a l c o o l - i . e . , amount of a l l o y p e r 50 p c t i n c r e a s e in the m u l t i -
ing t i m e and c r i t i c a l cooling r a t e on a l l o y content is p l y i n g f a c t o r . As can be s e e n , the a - s t a b i l i z e r s r e -
shown in F i g s . 12 and 13. Again, the b e h a v i o r of m o - q u i r e much l e s s a l l o y i n g a d d i t i o n than the y - s t a b i l i z e r s
l y b d e n u m and s i l i c o n d i f f e r s f r o m that of the o t h e r e l e - for an e q u i v a l e n t i n c r e a s e in h a r d e n a b i l i t y .
m e n t s , a r e s u l t which is c o n s i s t e n t with the findings Although this p r o p o s a l s u g g e s t s that c e r t a i n a - s t a -
above. The a l l o y s a p p e a r to s e p a r a t e out a c c o r d i n g to b i l i z i n g e l e m e n t s , i . e . , Ti, V, Zr, C r , W, and Nb, i m -
whether they are substitutional austenite stabilizers, p r o v e the h a r d e n a b i l i t y of s t e e l , the c o m p e t i n g p r o c e s s
r e p r e s e n t e d b y Ni, Mn, Co, o r f e r r i t e s t a b i l i z e r s , i . e . , of c a r b i d e p r e c i p i t a t i o n in the a u s t e n i t e r o b s it of both
the y - loop f o r m e r s , Mo and Si. When the b a s i s of c o m - c a r b o n and a l l o y addition, thus l o w e r i n g h a r d e n a b i l i t y .
p a r i s o n is c r i t i c a l c o o l i n g r a t e to f o r m m a r t e n s i t e p e r H a r d e n a b i l i t y m u l t i p l y i n g f a c t o r r e s u l t s show that v a -
wt p c t a l l o y (slope of the two s t r a i g h t l i n e s in Fig. 13), n a d i u m I and t i t a n i u m 25 have f a c t o r s a p p r o a c h i n g 2 at
it is s e e n that the y - s t a b i l i z e r s have a s l o p e of 6000~ 0.03 p c t a l l o y a d d i t i o n s which a r e g r e a t e r than that of
p e r min p e r wt pct a l l o y w h e r e a s the a - s t a b i l i z e r s have m o l y b d e n u m , the m o s t effective a l l o y . Unfortunately,
a slope of 25,000~ p e r min p e r wt p c t a l l o y . T h a t i s , it b e y o n d 0.03 pct, t i t a n i u m o r v a n a d i u m c a r b i d e p r e c i p i -
is e a s i e r to f o r m m a r t e n s i t e o r i n c r e a s e h a r d e n a b i l i t y t a t i o n o c c u r s and the m u l t i p l y i n g f a c t o r b e g i n s to d r o p .
with the a - s t a b i l i z e r s .
Our r e s u l t s w e r e c o m p a r e d with the e a r l y h a r d e n -
SUMMARY
a b i l i t y d a t a of G r o s s m a n 1 and K r a m e r et a l . , 2 a s w e l l
a s with the l a t e r d a t a of K r a m e r et al. 21 and Manning The effect of cooling rate (10~ per min to 25,000~
et al. 22 The m u l t i p l y i n g f a c t o r s f r o m t h e s e i n v e s t i g a - per min) on the transformation of austenite to pearlite
tions t a k e n at 0.45 wt p c t a r e l i s t e d in T a b l e H. The and martensite in a eutectoid binary Fe-0.8 pct C alloy
t r e n d s shown b y t h e s e r e s u l t s , p a r t i c u l a r l y t h o s e of and ternary Fe-C eutectoid alloys with Mo, Mn, Ni, Co,
Manning et al. z2 a r e in a g r e e m e n t with our findings, and Si was studied by means of hot-stage cinephotomi-
e x c e p t for s i l i c o n , which we found h a s a g r e a t e r effect crography. Continuous cooling transformation diagrams
on h a r d e n a b i l i t y b a s e d on its C - T d i a g r a m b e h a v i o r . were constructed, and critical cooling rates, i.e., the
The b r e a k d o w n of the a l l o y s into a - s t a b i l i z e r s and cooling rates necessary to form martensite, were used
y - s t a b i l i z e r s is in q u a l i t a t i v e a g r e e m e n t with the c o n - to determine the effect of the alloys in improving hard-
c e p t of the two a l l o y c l a s s e s f i r s t p r o p o s e d by Z e n e r . 24 enability. These determinations provided the basis for
He s t a t e d that one c l a s s r e t a r d e d the f o r m a t i o n of both dividing the alloys into two groups:
p e a r l i t e and b a i n i t e , with m a n g a n e s e and n i c k e l b e i n g 1) The a-stabilizers, Mo and Si.
a m o n g the m o s t p r o m i n e n t in this c l a s s . Z e n e r noted 2) The y-stabilizers, Mn, Ni, and Co.
that the s e c o n d c l a s s which i n c l u d e s m o l y b d e n u m , r e - The a-stabilizers showed the strongest effect in im-
t a r d s the f o r m a t i o n of only p e a r l i t e , a p h e n o m e n o n proving hardenability.
which he b e l i e v e d is ~tssociated with the c a r b i d e - f o r m - The hot-stage technique is ideally suited for harden-
ing t e n d e n c i e s of t h i s c l a s s . ability studies since thermal, kinetic, and morphologi-
The d e g r e e of p o t e n c y of the a - s t a b i l i z e r s and y - cal data can be obtained simultaneously for the trans-
s t a b i l i z e r s is shown in T a b l e III w h e r e h a r d e n a b i l i t y formation of austenite into one or more of its trans-
is c o m p a r e d using a m e t h o d p r o p o s e d b y G r o s s m a n , 1 formation products.

METALLURGICAL TRANSACTIONS V O L U M E 4, O C T O B E R 1 9 7 3 - 2 2 9 9
 i.~1or r!loo

IZ~K izso

I~O( IZOO

I15( 115o
- - - 9 ~

IIC'{ riO 9
Ii.

~ ;OSC ~loso

~,~
-\
SI ~--$.10o
9 -O 3 %

9 -0 46%
9 -3 35 %
go( G~

i ( J I . . . . . . . . I . . . . . . . . .
75(
....... i00 iooo PO. ~ 4 0 I00,000 I00 I~ ~.000 uoa~
COOLING RATE.*F/min COOLING RATE. *F/ 9

(a)
(e)
Fig. 9--The effect of cooling r a t e on the t r a n s f o r m a t i o n t e m -
p e r a t u r e of t e r n a r y eutectoid F e - C alloys containing: (a) 0.46
J~oc
pct and 3.35 pct Ni, (b) 0.43 pct and 0.78 pct Mn, (c) 0.49 pct
125{ and 1.00 pct Co, (d) 0.23 pct and 0.45 pct Mo, and (e) 0.30 pct
120( Si.
ii${

0 - o 4 3 Ain

- o 4ql m
M~n 130(
D-04SMo
9 -0.43%
9 -0 78% i1-04S Co

9 - 0 3 0 S*
. . . . i . . . . . . . . . . . . . . . . . , . . . . . . . . 120(
9 '' IOO IOOO I0,000 IO0

COOLING RATE. "F/ram

(b) IiO(

1300

115r es(

i~ I I0r 8o . . . . . . . . i . . . . . . . . . . . . . . . . . .
to . . . . . . . . I00 i000
TIME, IIr
o~ IO5C

Fig. 10--Continuous cooling t r a n s f o r m a t i o n d i a g r a m s for the

t e r n a r y eutectoid alloys at a constant concentration of 0.45 wt
pct, except for silicon, which was only a 0.3 wt pct addition.

9 -OIG% ~,~.. i 3 , ~
9 - l 00% \
e~

ioo I0O0 Io.ooo

COOLING RATE ."IF/min

i~1or

V - NI

0-$1
130(
X - Co

IZ~ 12or Q-M,

IZC~ X Z~-Ma

o~. l i e
115(

u. I IO(
i
* IlO{
Z
I05(

~,~
\
~'~ 9~

Z 3 4 S e 7 g
ALLOY
S I0 II 12
CONCENTRATION. w/o
13 14 IS 33S

....... ;o ' ...... ;ooo . . . . . . . ,;~,oo

COOLING RATE, *F/ 9
Fig. 11--The effect of alloy concentration on the t r a n s f o r m a -
(d) tion t e m p e r a t u r e at a constant cooling r a t e of 10~ p e r 9

2300-VOLUME 4, OCTOBER 1973 METALLURGICAL TRANSACTIONS

 ,, ACKNOWLEDGMENTS

T h e a u t h o r s w i s h t o e x p r e s s a p p r e c i a t i o n t o J . R.
K i l p a t r i c k , A. O. B e n s c o t e r , R. E . S t e i g e r w a l t , J . C.
z( H l u b i k , W. A. B e v e r i d g e , a n d P. M. G i l e s . T h e a u t h o r s
a l s o a p p r e c i a t e t h e a s s i s t a n c e of B. S. M i k o f s k y f o r
h i s i n p u t in t h e p r e p a r a t i o n o f t h i s m a n u s c r i p t .
-. ";"i
z
p
-i
REFERENCES

1. M. A. Grossmann Trans. TMS-A1ME, 1942, vol 150, p. 227.

2. I. R. Kramer, R. H. Hafner, and S. L. Toleman Trans. TMS-AIME, 1944, vol
158, p 138.
3 W. Crafts and J. L. Lamont Trans. TMS-AIME, 1944, vol. 158, p. 157.
4 "Symposium on Hardenabdlty," October 1945, Trans. TMS-AIME, 1946, voh
ALLOY CONCENTRATION, w / o 167, p. 599.
5. Isothermal Transformation Diagrams, U. S. Steel, 1963.
Fig. 1 2 - - P l o t of the effect of alloy c o n c e n t r a t i o n v s c r i t i c a l
6 C. A. Liedholm MetalProgr., 1944, vol. 45, p. 95.
t i m e , d e m o n s t r a t i n g the c o n t r a s t i n g b e h a v i o r of f e r r i t e and
7. W. Steven and C. Mayer JISI, 1953, vol. 147, p. 33
austenite stabilizers,
8. D. J. Bhckwede and R. C. Hess Trans ASM, 1957, vol. 49, p. 427.
9. B. L. Bramfitt and A. R. Marder IMSProc., 1968, p. 43.
10. E. G. Bain and H. W. Paxton. Alloying Elements m Steel, ASM, 1961, 2nd ed.,
p. 112.
0 -S~
11. A. S. Yue Met. Trans., 1970, vol. 1, p 19
X -co 12. A. O. Benscoter, J. R. Kilpatrick, R. P. Wolf, and A. R. Marder. Microstructures,
[3 - U .
1970, vol. 1, p. 25.
ZZ - M e
13 A. R. Marder and G. Krauss Trans. ASM, 1969, vol. 62, p. 957.
14. G. R. Speich and M. Cohen: Trans. TMS-AIME, 1960, vol. 218, p. 1050.
15. G. R. SpeJch: Decomposition of Austenite by Dlffuslonal Processes, lnterscmnce,
1962, p. 353.
16. R. H. Goodenon, S. J. Matas, and R. F. Hehemann' Trans TMS-AIME, 1963,
vol. 227, p. 651.
17. J. H. Frye, E. E. Stansbury, and D. L. McElroy Trans. TMS-AIME, 1953, vol
197, p. 219.
P 18. F. C. Hull, R. A. Colton, and. R. F. Mehh Trans. TMS-AIME, 1942, vol. 150,
~a Stabmz*rl a iz*. p 185.
19. J. W. Cahn and W. C. Hagel: ActaMet., 1963, vol. 11, p. 561.
20. D. Brown and N. Ridley: JISI, 1969, vol 207, p. 1232.
21. I. R. Kramer, S. Siegel, and J. G. Brooks Trans. TMS-AIME, 1946, vol. 167,
p. 670.
I0 ZO 30 40
22. R. D Manning, H. M. Reichhold, and J. M. Hodge' Sympostum Transformation
ALLOY CONCENTRATION, wlo
and Hardenability in Steels, Chmax Moly. Co., 1967, p. 169
Fig. 1 3 - - P l o t of the effect of alloy c o n c e n t r a t i o n vs c r i t i c a l 23. J. H. Hollomon and L. D. Jaffe" Trans. TMS-A1ME, 1946, vol. 167, p. 601.
c o o l i n g r a t e , d e m o n s t r a t i n g the c o n t r a s t i n g b e h a v i o r of f e r - 24. C. Zener: Trans. TMS-AIME, 1946, vol. 167, p. 550.
r i t e and a u s t e n i t e s t a b i l i z e r s . 25. G. F. Comstock: Trans. TMS-AIME, 1946, vol. 167, p. 719.

METALLURGICAL TRANSACTIONS VOLUME 4, OCTOBER 1973-2301