Measurement and Interpretation

of Isothermal Martensitic Kinetics

V. R A G H A V A N A N D M O R R I S C O H E N

A b r i e f s u r v e y of experimental work on isothermal martensitic transformations i s given.

R e c e n t r e s u l t s on quantitative metallography a r e presented. M o d e l s for the i s o t h e r m a l kinet-
ics a n d t h e m e t h o d o f e v a l u a t i n g t h e a u t o c a t a l y t i c f a c t o r as well a s t h e a c t i v a t i o n f r e e e n e r g y
for nucleation are d i s c u s s e d . T h e l i n e a r dependence of the activation e n e r g y on the c h e m i c a l
f r e e - e n e r g y i s f o u n d t o e x t r a p o l a t e s a t i s f a c t o r i l y t o t h e l o w M s t e m p e r a t u r e s e x h i b i t e d by
F e - N i a l l o y s . T h e v a l u e s o b t a i n e d by s u b s t i t u t i n g t h e a b o v e e m p i r i c a l l y - d e t e r m i n e d p a r a m -
e t e r s into t h e K a u f m a n - C o h e n n u c l e a t i o n e q u a t i o n i n d i c a t e t h a t t h e e m b r y o s i n F e - N i a l l o y s
a r e m o r e p o t e n t t h a n t h o s e in F e - N i - M n a l l o y s , w h e r e a s t h e i n t e r r a c i a l e n e r g i e s a r e q u i t e
similar.

M A R T E N S I T I C t r a n s f o r m a t i o n s in i r o n - b a s e a l l o y s with a substantial amount of martensite b e i n g f o r m e d

h a v e r e c e n t l y been c l a s s i f i e d a c c o r d i n g t o t h e ob-
s e r v e d k i n e t i c b e h a v i o r . I n one o f t h e c l a s s i f i c a t i o n s , *
t h e t r a n s f o r m a t i o n s f a l l into t h r e e c a t e g o r i e s . T h e
f i r s t o f t h e s e is t h e well-known a t h e r m a l t r a n s f o r m a -
t i o n , w h e r e the p r o g r e s s of t h e r e a c t i o n d e p e n d s m a i n -
ly o n f a l l i n g t e m p e r a t u r e . T h e s e c o n d g r o u p i n c l u d e s
certain F e - N i and F e - N i - C a l l o y s with transformation
r a n g e s at s u b z e r o t e m p e r a t u r e s , w h e r e t h e r e a c t i o n is
i n i t i a t e d by a n a b r u p t b u r s t . A l s o , i n t h i s t e m p e r a t u r e
r a n g e , we h a v e t h e t h i r d c a t e g o r y o f c o m p l e t e l y -
i s o t h e r m a l b e h a v i o r , a s e x h i b i t e d by F e - N i - M n a n d
F e - N i - C r alloys.
Another type of classification 2 a s s o c i a t e s the a t h e r -
mal behavior with dynamic stabilization. In that con-
text, the burst and the completely-isothermal t r a n s -
f o r m a t i o n s are g r o u p e d t o g e t h e r as " i s o t h e r m a l , " t h e
c o m m o n feature between them b e i n g the a b s e n c e of
concurrent stabilization.
B a s e d on r e c e n t f i n d i n g s , R a g h a v a n a n d C o h e n 3 h a v e
redefined t h e transformation behavior at s u b z e r o t e m -
p e r a t u r e s in t h e f o l l o w i n g m a n n e r . T h e y h a v e n o w
s h o w n that a completely isothermal transformation to
l e n t i c u l a r m a r t e n s i t e o c c u r s in a n F e - ~ 2 9 N i * a l l o y
*Weight percentages are given throughout the text, unless otherwise indicated.
within a n a r r o w temperature r a n g e , a n d this i s o t h e r -
m a l b e h a v i o r is m e a s u r a b l e f r o m t h e v e r y b e g i n n i n g
of the t r a n s f o r m a t i o n . O n q u e n c h i n g t h e s a m e a l l o y t o
s t i l l l o w e r temperatures, however, transformation
d u r i n g c o o l i n g t o t h e t e s t t e m p e r a t u r e c a n n o t be
avoided, a n d t h e t e r m " a n i s o t h e r m a l " is a d o p t e d h e r e
to d e s c r i b e such r e a c t i o n k i n e t i c s . T h e t r a n s f o r m a -
t i o n u n d e r s u c h c o n d i t i o n s i s t h e r m a l l y a c t i v a t e d , but
t h e a c t i v a t i o n e n e r g i e s f o r n u c l e a t i o n a r e t h e n so l o w
that t h e t r a n s f o r m a t i o n r a t e s c a n n o t be m e a s u r e d e x -
perimentally. In the same F e - N i alloy, b u r s t s with an
a u d i b l e c l i c k o c c u r o n q u e n c h i n g w e U into t h i s r a n g e ,
V. RAGHAVAN and MORRIS COHEN are Research Associate and
Ford Professor of Materials Science and Engineering, respectively,De-
partment of Metallurgy and Materials Science, Massachusetts Institute
of Technology, Cambridge, Mass.
This paper is based on an invited talk presented at a symposium on
Formation of Martensite in Iron Alloys sponsored by the IMD Ferrous
Metallurgy Committee and held at the Spring Meeting of T h e Metal-
lurgical Society of AIME, May 1 9 7 0 , in Las Vegas, Nev.
i n t h e o r d e r o f m i c r o s e c o n d s , a, 5 A t s t i l l l o w e r t e m -
p e r a t u r e s , t h e true a t h e r m a l mode ( i . e . , t r a n s f o r m a -
t i o n w i t h o u t t h e r m a l a c t i v a t i o n ) p r e v a i l s , at l e a s t in
p r i n c i p l e , a n d c o r r e s p o n d s to t h e s i t u a t i o n w h e r e t h e
extrapolated activation e n e r g y for nucleation goes t o
zero.
I n a l l o y s c o n t a i n i n g m o r e t h a n 30 p c t N i , t h e i n i t i a -
t i o n o f t h e t r a n s f o r m a t i o n w i t h a b u r s t is i n t e r p r e t e d
a s an e x t r e m e form of autocatalysis, even though the
transformation may s t i l l r e q u i r e some t h e r m a l a c t i -
vation,s
I n t h e p r e s e n t p a p e r , we a r e c o n c e r n e d w i t h c o m -
pletely isothermal behavior and its interpretation on
the b a s i s of a nucleation m o d e l . T h e o v e r a l l t r a n s f o r -
m a t i o n k i n e t i c s a r e b e i n g t r e a t e d i n t h i s S y m p o s i u m by
A. R. Entwisle.
B R I E F SURVEY O F EXPERIMENTAL WORK
ON ISOTHERMAL MARTENSITE
T h e isothermal mode of t h e martensitic t r a n s f o r m a -
t i o n is n o w well d o c u m e n t e d . * , 3, 6 - ~ K u r d j u m o v a n d
Maksimova% 7 were t h e f i r s t t o r e p o r t isothermal
m a r t e n s i t e in a n u m b e r o f s t e e l s a n d i r o n - b a s e a l l o y s .
T h e y f o u n d , f o r e x a m p l e , t h a t in a 1 . 6 C s t e e l , i s o -
t h e r m a l transformation o c c u r s at t e m p e r a t u r e s b e l o w
- 1 0 0 ~ C . M o r e o v e r , i n a 0 . 6 C - 6 M n - 2 C u s t e e l6 a n d i n
an Fe-23Ni-3.4Mn alloy,7 the isothermal t r a n s f o r m a -
tion exhibits C - c u r v e behavior. Both of t h e s e a l l o y s
c a n be q u e n c h e d t o - 196 ~ C w i t h o u t a n y t r a n s f o r m a -
t i o n , but t h e y s t a r t t o t r a n s f o r m o n r e h e a t i n g . T h e
m a x i m u m initial r a t e of transformation t a k e s p l a c e
a r o u n d - 1 3 0 ° C . T h e total quantity of i s o t h e r m a l m a r -
t e n s i t e o b s e r v e d is also a m a x i m u m at t h i s t e m p e r a -
ture.
D a s G u p t a a n d L e m e n t~ n o t e d t h a t , i n a 0 . 7 C - 1 5 C r
s t e e l , i s o t h e r m a l t r a n s f o r m a t i o n is a l w a y s p r e c e d e d
by s o m e a t h e r m a l t r a n s f o r m a t i o n a n d p r o g r e s s e s by
t h e f o r m a t i o n o f n e w l e n t i c u l a r p l a t e s r a t h e r t h a n by
the growth of existing o n e s .
K u l i n a n d S p e i c h~ s t u d i e d t h e i s o t h e r m a l t r a n s f o r -
m a t i o n in a n F e - 1 4 C r - 9 N i a l l o y , a n d s h o w e d t h a t t h e
transformation follows C - c u r v e kinetics with a m a x i -
mum r a t e at - 35°C. T h e initial m a r t e n s i t e c o n t e n t at
the s t a r t of the i s o t h e r m a l runs v a r i e s b e t w e e n 0 and

METALLURGICAL TRANSACTIONS VOLUME 2 , SEPTEMBER 1971-2409

23 p c t . T h e Ms i n t h i s a l l o y i s d e p e n d e n t on t h e c o o l -
i n g r a t e ; s o m e m a r t e n s i t e m a y be f o r m e d i s o t h e r m a l -
ly a b o v e t h e M s . *
*In the terminology adopted here, this type of reported Ms temperature is re-
garded as the beginning of the anisothermal transformation at the given cooling
rate.
M a c h l i n a n d C o h e n1° p r e q u e n c h e d a n F e - 2 9 N i a l l o y
into liquid nitrogen, b e f o r e m e a s u r i n g the isothermal
transformation at v a r i o u s h i g h e r holding t e m p e r a -
t u r e s . By t h i s p r o c e d u r e , t h e y w e r e able t o s t u d y t h e
isothermal kinetics at a c o n s t a n t fraction o f p r i o r
martensite. The isothermal rate had an interpolated
m a x i m u m at - 140°C. Recently, Anandaswaroop a n d
Raghavan n employed a s i m i l a r alloy and p r o c e d u r e t o
m e a s u r e the isothermal nucleation r a t e s upon r e h e a t -
i n g f r o m a p r e q u e n c h i n g t e m p e r a t u r e o f - 9 5 °C; u n d e r
t h e s e conditions, the m a x i m u m rate o c c u r s a t - 7 0 ° C .
C e c h a n d H o l l o m o n12 r e p o r t e d o n t h e i s o t h e r m a l
t r a n s f o r m a t i o n b e t w e e n - q9 o a n d - 196 ° C i n a n F e -
23Ni-3.7Mn alloy. T h e transformation exhibited typi-
cal C - c u r v e behavior, with t h e nose temperature at
- 130 ° C , t h u s c o n f i r m i n g t h e f i n d i n g s o f K u r d j u m o v
and Maksimova. 7 At each holding temperature, the
transformation r a t e w a s a m a x i m u m initially, a n d de-
c r e a s e d as t h e reaction p r o g r e s s e d . A s u r f a c e l a y e r
o f h i g h e r m a r t e n s i t e c o n t e n t w a s f o r m e d to a d e p t h o f
0 . 0 0 2 to 0 . 0 0 5 i n . d u r i n g t h e i s o t h e r m a l t r a n s f o r m a -
t i o n , a n d was a t t r i b u t e d to t h e d e p l e t i o n o f m a n g a n e s e
or c a r b o n from the s u r f a c e d u r i n g the austenitizing
s u b s e q u e n t i s o t h e r m a l t r a n s f o r m a t i o n r a t e is a m a x i -
mum initially a n d t h e n d e c r e a s e s with t i m e . T h u s , it
b e c o m e s c l e a r that t h e b a s i c c h a r a c t e r i s t i c s o f t h e
i s o t h e r m a l r e a c t i o n a r e best s t u d i e d in t h e a b s e n c e o f
a n y p r i o r m a r t e n s i t e , e i t h e r at t h e s u r f a c e o r in t h e
b u l k . R e c e n t l y , E n t w i s l e14 a n d P a t i a n d C o h e n i s c o n -
f i r m e d t h i s s i g n i f i c a n t p o i n t i n a n u m b e r of F e - N i - M n
alloys.
P h i l i b e r t a n d C r u s s a r d16 f o u n d t h a t , i n a 1 . 4 C -
2 . 5 C r s t e e l , l i m i t e da m o u n t s of isothermal martensite
may form a f t e r the r e g u l a r cooling transformation. In
a d d i t i o n , P h i l i b e r t 17 n o t e d t h a t i f a n F e - 2 9 N i a l l o y i s
cooled step-by-step, each hold g i v e s an i s o t h e r m a l
c u r v e w i t h a t r a n s f o r m a t i o n r a t e w h i c h is s l o w at
f i r s t , a n d t h e n i n c r e a s e s w i t h t i m e b e f o r e f a l l i n g off
a g a i n . H e also s h o w e d t h a t , if t h e c a r b o n a n d n i t r o g e n
a r e sufficiently low, t h e b u r s t c h a r a c t e r o f t h e t r a n s -
f o r m a t i o n d i s a p p e a r s a n d isothermal mode o c c u r s at
h i g h e r t e m p e r a t u r e s . In line with t h e s e r e s u l t s , W o o -
d i l l a , W i n c h e l l , a n d C o h e n18 d e m o n s t r a t e d t h a t s t a b i l i -
zation effects d i s a p p e a r on decarburization. S i m i l a r l y ,
Y e o 19 f o u n d t h a t , i n t h e p r e s e n c e of a s t r o n g c a r b i d e -
f o r m i n g e l e m e n t s u c h a s t i t a n i u m , t h e s t a b i l i z a t i o n due
7o l,ot_ /.022 /
60 t-o.5 i- /
ol ~ , , i , l I |

treatment. 50 0 iO0 ZOO rain 0084

S h i h , A v e r b a c h , a n d C o h e n13 d e s i g n e d e x p e r i m e n t s
t o a v o i d t h e p r e s e n c e o f s u r f a c e m a r t e n s i t e at t h e •~ 4 0 - / _ . . ~ .
s t a r t o f t h e isothermal r u n , a n d s h o w e d t h a t (in t h e
a b s e n c e of any p r i o r martensite) the initial isothermal 30 ___..-- o.o~l
transformation i s q u i t e slow compared t o the a c c e l -
e r a t e d r a t e o b s e r v e d as t h e reaction p r o g r e s s e s . T h e 20 / ~ o . 0 4 3
reaction rate then d e c r e a s e s d u r i n g the l a t e r s t a g e s of
the t r a n s f o r m a t i o n . I s o t h e r m a l t r a n s f o r m a t i o n c u r v e s I0
t y p i c a l o f such b e h a v i o r a r e s h o w n in Fig. 1. How-
e v e r , t h e c u r v e s m a y be v e r y d i f f e r e n t i n s h a p e i f t h e 0 I I I
0 20 40 60 80 I00 120 140 160 180
t r a n s f o r m a t i o n is d e t e r m i n e d a f t e r s o m e m a r t e n s i t e
Time, min
i s f o r m e d by p r e - q u e n c h i n g into l i q u i d n i t r o g e n . D u e
to t h e s t i m u l a t i n g e f f e c t o f t h e p r i o r m a r t e n s i t e , t h e Fig. 2--Isothermal transformation c u r v e s a t - 6 6 ° C f o r F e -
26Ni-2Mn a l l o y a s a function of g r a i n s i z e . G r a i n d i a m e t e r s
( m m ) a r e indicated on c u r v e s . l

60L T F ] F
~zi- / -t
30 -

50

~ 20 ,0 - -,2o°c - ~40
G
~ 15 o "E30 - 20.0"C--
o

,o7//// / / /J" 20 1 8 . 0 o c-
II/// / / o;
_

10
0 "196°C
0 I0 20 30 40 50 60 7 0 80 90 I 0 0 I10
T i m e , mir~. 20 40 60 80 I00 120 140 160 180
Time, rain
Fig. 1--Isothermal transformation c u r v e s for Fe-23Ni-3.6Mn
a l l o y a t i n d i c a t e d t e m p e r a t u r e s f o r s a m p l e s containing no ini- F i g . 3--Isothermal transformation c u r v e s for F e - 2 9 . 2 N i -
tial martensite. I n s e r t f i g u r e s h o w s the e a r l y t r a n s f o r m a - 0.2Mn a l l o y a t i n d i c a t e d t e m p e r a t u r e s f o r s a m p l e s containing
tion. 13 no initial m a r t e n s i t e f l

2410-VOLUME2, SEPTEMBER 1971 METALLURGICAL TRANSACTIONS

t o c a r b o n i s a b s e n t , a n d t h e n a n F e - 2 5 N i a l l o y c a n be microstructure, often seen a f t e r isothermal t r a n s f 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 to o v e r 9 0 p c t o f m a r t e n - m a t i o n at - 2 2 ° C , a r e s h o w n in Fig. 5 . T h e p r e d o m i -
site. n a n c e of t h i c k , m i d r i b p l a t e s i s e v i d e n t . T h e b o u n d -
Raghavan and Entwisle I investigated the isothermal a r i e s b e t w e e n t h e s e p l a t e s a r e n o t well defined. M a r k -
t r a n s f o r m a t i o n in a n F e - 2 6 N i - 2 M n a U o y . E v e n t h o u g h i n g s n e a r t h e m i d r i b r e g i o n , i d e n t i f i e d e a r l i e r2° a s i n -
t h i s a l l o y d i s p l a y s t h e i s o t h e r m a l m o d e o v e r a wide t e r n a l twins, a r e also o b s e r v e d .
r a n g e o f t e m p e r a t u r e s ( b e t w e e n - 60 ° a n d - 100 ° C ) , i t Thick, midrib p l a t e s h a v i n g more clearly d e f i n e d
c o u l d not be q u e n c h e d into l i q u i d n i t r o g e n w i t h o u t t h e boundaries, a n d s h o w i n g twin m a r k i n g s n e a r t h e mid-
e n t r e e o f a b u r s t . Typical transformation c u r v e s at r i b r e g i o n with i n c r e a s i n g frequency, b e g i n t o d o m i -
- 6 6 ° C obtained with different austenitic g r a i n s i z e s n a t e t h e w h o l e m i c r o s t r u c t u r e in s p e c i m e n s q u e n c h e d
a r e p l o t t e d in Fig. 2. T h e i r i n t e r p r e t a t i o n o f t h i s a few d e g r e e s b e l o w - 2 2 ° C . At t h e s e t e m p e r a t u r e s ,
g r a i n - s i z e e f f e c t o n t h e i s o t h e r m a l t r a n s f o r m a t i o n is t h e t r a n s f o r m a t i o n is t o o r a p i d to m e a s u r e i s o t h e r -
d i s c u s s e d in a l a t e r s e c t i o n . mally. Whatever the crystallographic interpretation
R e c e n t l y , R a g h a v a n a n d C o h e n3 m e a s u r e d t h e i s o - o f t h e s e p r o g r e s s i v e changes m a y be, t h e y t a k e p l a c e
thermal-transformation kinetics without p r i o r m a r t e n -
s i t e in two b i n a r y F e - N i a l l o y s . Fig. 3 i l l u s t r a t e s t h e
isothermal t r a n s f o r m a t i o n as a function o f reaction
temperature for an Fe-29.2Ni-0.21Mn-0.006C alloy.
T h e t i m e t o f o r m 0.1 p c t m a r t e n s i t e ( m i n i m u m d e t e c t -
able a m o u n t ) is l i s t e d in T a b l e I . T h e t r a n s f o r m a t i o n
is v e r y s e n s i t i v e t o t h e t e s t t e m p e r a t u r e , b e i n g b a r e l y
d e t e c t a b l e a t - 1 4 . 5 ° C a n d b e c o m i n g too f a s t t o m e a s -
ure isothermally b e l o w - 2 2 ° C . Fig. 4 illustrates t h e
microstructure o b t a i n e d by i s o t h e r m a l t r a n s f o r m a t i o n
at - 1 8 ° C ; t h e m o r p h o l o g y is c l e a r l y l e n t i c u l a r w i t h
some of the plates containing b a r e l y v i s i b l e m i d r i b s .
T h e m i d r i b f r e q u e n c y in t h i s a l l o y i n c r e a s e s w i t h de-
c r e a s i n g reaction temperature, and b e c o m e s a s i g n i f -
icant feature o f t h e microstructure at t h e l o w e s t iso-
t h e r m a l temperature ( - 22°C). S e l e c t e d a r e a s of the

Table I. Time to Form the First Detectable Martensite (t0.j)

as a Function o f the Isothermal.Reaction Temperature, T (Ref. 3)

T, °C to.t, sec
- 14.5 2400
-16.0 1200
-17.0 510
-18.0 162
-20.0 55
-22.0 27

Fig. 5--Selected a r e a in the m i e r o s t r u c t u r e obtained by i s o -

t h e r m a l transformation a t - 2 2 ° C of Fe-29.2Ni-0.2Mn alloy.
T h e predominance of thick, m i d r i b p l a t e s i s evidentfl

l i I I i ~ I I I I /

60 OO

40 3 °C-
• e °c
'~ 3 0

2011 / / _ _ _ - - - - - - 8 °C -

0 20 40 60 8 0 100 120 140 160 180

Time, rain
Fig. 4 - - M i c r o s t r u c t u r e obtained by i s o t h e r m a l transformation F i g . 6--Isothermal transformation c u r v e s for F e - 2 8 . 8 N i a l l o y
a t - 1 8 ° C of Fe-29.2Ni-0.2Mn alloy. 3 at indicatedtemperatures.3

METALLURGICAL TRANSACTIONS VOLUME 2 , SEPTEMBER 1971-2411

w i t h o u t a n y a p p a r e n t d i s c o n t i n u i t y in t h e k i n e t i c s . I n
o t h e r w o r d s , t h e r e is n o a b r u p t k i n e t i c t r a n s i t i o n c o r -
responding to the i n c r e a s i n g concentration of m i d r i b s
in t h e m i c r o s t r u c t u r e . *
*On quenching to still lower temperatures, this alloy begins t o transform in a
burst with an audible click.
Fig. 6 i n d i c a t e s t h e i s o t h e r m a l t r a n s f o r m a t i o n in a n
F e - 2 8 . 8 N i - 0 . 0 0 2 C alloy as a function o f reaction t e m -
perature. This alloy t r a n s f o r m s t o n e a r l y 60 pct of
m a r t e n s i t e a t 0 ° C . A s h a s b e e n n o t e d p r e v i o u s l y , 21, 22
t h e n i c k e l c o n t e n t of t h i s a l l o y i s j u s t a b o u t a t t h e
transition between nonlenticular and lenticular mor-
p h o l o g y . C o r r e s p o n d i n g l y , t h e m i c r o s t r u c t u r e in
Fig. 7 exhibits a m i x t u r e o f nonlenticular a n d lenticu-
lar martensite f o r m e d o n isothermal transformation
at 6°C. T h e n o n i e n t i c u l a r m a r t e n s i t e is o f t h e l a t h ( o r
p a c k e t ) t y p e , a n d is p r o d u c e d i s o t h e r m a l l y , a s is t h e
lenticular martensite, u n d e r t h e s e conditions.
QUANTITATIVE METALLOGRAPHIC
MEASUREMENTS
Pati and Cohen~5 employed quantitative metallo-
graphic techniques for measuring nucleation rates
during isothermal martensitic transformations. At
any given reaction temperature, they transformed a
series of samples to various extents, and obtained the
number of martensitic plates per unit test volume
(Nu) in each specimen by Fullman's equation:23
8 E NA
gv - ~-2
w h e r e NA i s t h e n u m b e r o f p l a t e s p e r u n i t a r e a of r a n -
d o m t e s t p l a n e , a n d E i s t h e m e a n r e c i p r o c a l of t h e
p l a t e l e n g t h s a s i n t e r s e c t e d by a r a n d o m p l a n e .
T h e m e a n v o l u m e o f t h e p l a t e s ~ up t o a n y g i v e n
s t a g e o f t r a n s f o r m a t i o n is s i m p l y :
~) = f / N v
Fig. 7--Mierostructure obtained by isothermal transforma-
tion at 6°C of Fe-28.8Ni alloy, showing both lenticular and
nonlenticular morphologies. Arrows indicate surface tilts
due to spontaneous transformation on the electropolished
s u r f a c e .3
2412-VOLUME 2 , SEPTEMBER 1971
15.0 I I I I I I I I
12.5 -
I 0 . 0 -
o
Q 7.5-
v
z 5.0-
25-
0
50 I00 150 200 250 500 550 400 450
T i m e , sec
Fig. 8--Number of martensitic plates formed per unit test
volume (Nv), as a function of transformation time at -115°C
in Fe-24Ni-3Mn alloy.24
w h e r e f is t h e v o l u m e f r a c t i o n o f m a r t e n s i t e , a n d c a n
be d e t e r m i n e d by p o i n t c o u n t i n g .
T h e nucleation r a t e s are evaluated directly f r o m
t h e s e m e a s u r e m e n t s . Fig. 8 is a p l o t o f N v a s a f u n c -
tion of transformation time for an Fe-24Ni-3Mn alloy
r e a c t e d at - 1 1 5 ° C . T h e nucleation r a t e at a n y instant
is o b t a i n e d f r o m t h e s l o p e o f t h i s p l o t :
~_ dNu 1
at 1 - f [3]
[1] It i s e v i d e n t t h a t t h e n u c l e a t i o n r a t e i n c r e a s e s a p p r e -
c i a b l y d u r i n g the initial part of the transformation
( a u t o c a t a l y s i s ) a n d t h e n d e c r e a s e s d u r i n g the l a t e r
s t a g e s . P a t i a n d C o h e n24 a l s o d e v e l o p e d k i n e t i c e q u a -
tions to generate the transformation c u r v e s , taking the
a u t o c a t a l y t i c e f f e c t s into a c c o u n t a s d e s c r i b e d i n a
l a t e r section.
[2]
SURFACE NUCLEATION
The importance of measuring the isothermal trans-
formation in the absence of prior martensite, either at
the surface or within the interior of the specimen, has
already been stressed. Apart from the fact that surface
martensite has morphological and crystallographic
characteristics2~, 28 different from those of bulk mar-
tensite, the fast nucleation rate at the surface inter-
feres with the measurement of the slower volume nu-
cleation during the early stages of transformation.
The surface martensite tends to stimulate the bulk
transformation by spreading inwards from the surface.
Therefore, it is desirable to avoid surface nucleation
for quantitative transformation studies in bulk sam-
pies.
The method currently used to achieve this end con-
sists of enriching the outer layers of the specimen
with a small amount of carbon, thus effectively sta-
bilizing the surface against preferential nucleation.
A suitable time-temperature combination is chosen
for the final austenitizing treatment such that the
right quantity of carbon is transferred to the speci-
men surface from a source.
Obviously, preferential surface nucleation can be
caused by inadvertent decarburization, but the phe-
nomenon is also associated with the free surface it-
METALLURGICAL TRANSACTIONS
s e l f , e . g . , the lack of three-dimensional constraint
o n t h e transformation shape-change at t h e s u r f a c e .
T h i s c o n d i t i o n c a n be o f f s e t , a t l e a s t i n p a r t , by m e a n s
of an electroplated l a y e r which acts t o constrain the
s u r f a c e , as d e s c r i b e d below.
S e v e r a l s a m p l e s of a n F e - 2 4 N i - 3 M n a l l o y w e r e
b a t c h - a n n e a l e d a t 9 0 0 ° C f o r 15 m i n i n a n a r g o n a t -
mosphere without a c a r b o n s o u r c e . One-half of t h e s e
s p e c i m e n s w e r e then t r a n s f o r m e d i s o t h e r m a l l y a t
- 1 0 0 ° C , after electropolishing off the s u r f a c e l a y e r s ;
s p e c i a l care w a s t a k e n d u r i n g all mechanical handling.
Metallographic examination r e v e a l e d t h e s e s a m p l e s
to h a v e a g r e a t e r c o n c e n t r a t i o n o f m a r t e n s i t e n e a r t h e
s u r f a c e t h a n in t h e i n t e r i o r . T h e o t h e r h a l f o f t h e s a m -
ples were e l e c t r o p o l i s h e d a n d t h e n e l e c t r o p l a t e d with
a 0.001-in. thick adherent l a y e r of nickel. None of
t h e s e s a m p l e s h a d a n y p r e f e r e n t i a l c o n c e n t r a t i o n of
m a r t e n s i t e n e a r t h e s u r f a c e . By t h e s a m e t o k e n , t h e
transformation r a t e s d u r i n g t h e initial s t a g e s were
a l w a y s s l o w e r in t h e p l a t e d s p e c i m e n s t h a n in t h e u n -
p l a t e d o n e s , a s i l l u s t r a t e d in Fig. 9. T h i s f i n d i n g i s
consistent with the deduction that preferential n u c l e a -
t i o n at t h e s u r f a c e can enhance t h e o v e r a l l t r a n s f o r -
mation r a t e .
MODELS FOR ISOTHERMAL KINETICS
I n t h e i s o t h e r m a l t r a n s f o r m a t i o n , t h e i n c r e a s e in
i n i t i a l t r a n s f o r m a t i o n r a t e i s due t o a u t o c a t a l y t i c n u -
cleation. T h e f i r s t martensitic plates p r o d u c e more
n u c l e a t i o n s i t e s t h a n t h e y c o n s u m e o r s w e e p out, a n d
t h i s adds to t h e s u b s e q u e n t t r a n s f o r m a t i o n r a t e . D i -
r e c t m e a s u r e m e n t s by q u a n t i t a t i v e m e t a l l o g r a p h y h a v e
c l e a r l y s h o w n15 t h a t t h e n u c l e a t i o n f r e q u e n c y i n c r e a s e s
with t i m e d u r i n g the e a r l y s t a g e s of isothermal t r a n s -
f o r m a t i o n . T h e subsequent d e c r e a s e in t r a n s f o r m a -
tion r a t e i s attributable t o the partitioning effect, i . e . ,
the v o l u m e f r a c t i o n t r a n s f o r m e d p e r n u c l e a t i o n e v e n t
progressively d e c r e a s e s , as t h e a u s t e n i t e is divided
into s m a l l e r and s m a l l e r pockets.
Raghavan and Entwisle 1 t o o k both t h e s e effects into
account t o give a quantitative interpretation of t h e iso-
t h e r m a l martensitic kinetics. T h e y proposed that the
n u m b e r o f a u t o c a t a l y t i c e m b r y o s g e n e r a t e d is p r o p o r -
tional to the v o l u m e fraction of martensite formed, and
I I I 1 I /
t h e y a d o p t e d t h e p a r t i t i o n i n g m o d e l o f F i s h e r et al.27
t o e s t i m a t e the m e a n p l a t e s i z e a s a f u n c t i o n o f f r a c -
tion transformed. The transformation rate was t a k e n
t o be t h e p r o d u c t o f t h e n u c l e a t i o n r a t e a n d t h e v o l u m e
fraction t r a n s f o r m e d per nucleation event, from w h i c h
__dr = A Wa ~
(hi + P f - N v ) ( 1 - f ) v e x p ( - - f f T/
dt
X rnq (1 _ f ) l + 1/m [4]*
*The (1 - ~ factor in Eq. [4] was omitted by Raghavan and Entwisle; 1 it can
be disregarded in the early stages of the transformation.
where
/= the fraction of martensite f o r m e d ,
t = t i m e in s e c o n d s
n i = n u m b e r of preexisting nucleation s i t e s or
e m b r y o s in t h e p a r e n t a u s t e n i t e ( e s t i m a t e d
a s 107 p e r c u c m ) ,
p = n u m b e r of autocatalytic e m b r y o s p r o d u c e d
p e r u n i t v o l u m e of m a r t e n s i t e ,
N v = n u m b e r o f m a r t e n s i t e p l a t e s per unit v o l u m e
of alloy,
v = lattice vibration frequency,
ZxW a = a c t i v a t i o n e n e r g y f o r n u c l e a t i o n a t t e m p e r a -
ture 21,
rn = t h i c k n e s s - t o - d i a m e t e r r a t i o of the m a r t e n -
s i t i c plates, and
q = a v e r a g e v o l u m e per g r a i n of austenite.
T h e percentage of martensite a s a function of t i m e
c a n be c o m p u t e d by n u m e r i c a l i n t e g r a t i o n of E q . [ 4 ] .
Both q a n d rn a r e m e a s u r e d m e t a l l o g r a p h i c a l l y , a n d
t h e n t h e u n k n o w n q u a n t i t i e s p a n d ~x Wa c a n be e v a l u -
a t e d by c u r v e - f i t t i n g t h e c a l c u l a t e d t o t h e e x p e r i m e n -
tal r e s u l t s . T h e c u r v e s thus computed a g r e e q u i t e
w e l l w i t h t h e e x p e r i m e n t a l d a t a up t o 8 t o 10 p c t t r a n s -
70
/

N o t plated 6O
12
50 ioo eoo 300 4oo 500 - - 0.083-
~ ~ T I r n~ e ' m i n 0072
o_

t-
3o //C_-<:==-- ....
o . . . . o.oo,
Nickel plated / ~ - - ~ 0045

4
¢ f ......
I
Oi L ~ I _J
0 20 40 60 80 I 0 0 120 140 160 180
0 ~ I Time, min
2 4 6
T i m e , rain Fig. 10--Comparison of experimental transformation c u r v e s
with those computed f r o m Eq. (4) for Fe-26Ni-2Mn a l l o y
Fig. 9--Effect of n i c k e l plating on i s o t h e r m a l m a r t e n s i t i e t r a n s f o r m e d a t - 6 6 ° C . G r a i n d i a m e t e r s (ram) a r e i n d i c a t e d
transformation a t -100 °C. on c u r v e s . 1

METALLURGICAL TRANSACTIONS VOLUME 2 , SEPTEMBER 1971-2413

formation, as shown in Fig. 10 for an Fe-26Ni-2Mn 24 I I I I I I Experlimental
alloy having a r a n g e of g r a i n sizes. With further Test temperature - 6 6 ° C
G r a i n size q = 1.95 X 10-7 cm 3 Curve
\ J
amounts of transformation, however, the derived p A W a (callmole) ~ _
curves fall below the experimental curvesj this dis- 20 o 3.r x ,o'° ,6,40 ~ _ ~ . ~ . o A
crepancy will be discussed l a t e r . • ,.e ,o'O ,.,o _ B
The parameter rn is known to vary as the transfor-
mation proceeds. For an Fe-24Ni-3Mn alloy, Pati and
Cohen15 found that 1 / m = 18 - 20f up to [ = 0.4, but
substituting this relationship into Eq. [4] results only
in a m i n o r improvement in the curve-fitting. jO
In o r d e r to make the above model more consistent N B
with the experimental observation that plates often
form in clusters during the e a r l y stages of transfor-
mation, Raghavan ~ considered a two-step process:
i) the i n c r e a s e with time of the n u m b e r of austenitic oo
J
g r a i n s in which first-plate nucleation takes place, and
ii) the progress of further transformation within such 0 2 4 6 8 IO 12 14 16
grains. Thus, the overall transformation rate becomes Time, rain
a function of both the spreading and filling-in p r o c - Fig. ll--Transformation curves for Fe-26Ni-2Mn alloy cal-
e s s e s which o c c u r simultaneously. The outward s p r e a d culated a) by taking the formation sequence of plates into ac-
of nucleation from a central g r a i n due to autocatalysis count, and b) by assuming a uniform distribution of plates at
all times, compared with the experimental curve.28
is compared w i t h the growth process in a typical nu-
cleation and growth reaction. Following the Johnson-
Mehl-Avrami treatment, an expression was obtained sequence of plates into account, and (B) by a s s u m i n g
for the number of g r a i n s w h e r e first-plate nucleation a uniform distribution of plates at all times, are p l o t -
has occurred (Ng):
ted a l o n g with the experimental c u r v e . C u r v e A
Ng = 1/q [1 - exp { - q n i u exp ( - A W a / R T)(2 t ' / t '3 matches the data up t o 13 pct transformation. The
disparity beyond this point has been shown by Pati and
+ 4 t 3 / t '~ + 3 t z / t ' + t)}] [5] Cohen24 t o stem from the F i s h e r partitioning f o r m u -
w h e r e t ' is the approximate time to nucleate the f i r s t la 27 which overestimates the number of martensitic
plate in an austenitic g r a i n which is stimulated from plates r e q u i r e d t o give a certain fraction of t r a n s f o r -
a c r o s s its g r a i n boundary. Assuming that the autocat- mation, especially beyond 20 pct martensite. This de-
alytic effect is of the same magnitude on both sides of duction is made possible by introducing additional ex-
the g r a i n boundary, and noting that the strained region perimental data obtained from quantitative-metallo-
around the f i r s t plate in a g r a i n impinges on six neigh- graphic measurements. The kinetic analysis is o u t -
boring grains, Raghavan ~ derived the following ex- lined below.
pression for t':
GENERATION OF TRANSFORMATION CURVES
t '~- 1 / { ( n i q + m q p / 6 ) v exp ( - L X W a / R T ) } [6] FROM METALLOGRAPHIC MEASUREMENTS
w h e r e p is the same autoeatalytie parameter that a p -
The mean volume per martensitic plate f o r m i n g at
p e a r s in Eq. [4]. The transformation rate within any any instant during isothermal transformation cannot
one g r a i n is then equal to: be determined by d i r e c t measurements. On the o t h e r
hand, it is quite feasible to obtain the mean v o l u m e
dfg / d t = (niq + qpfg - P )(1 - f g ) exp ( - A W a / R T ) m (~) per plate of all the plates present at any t i m e .
This is done by r e a c t i n g a s e r i e s of specimens to dif-
× (1 -- f g ) l + 1/m [7]
ferent amounts of martensite at a constant holding
where f g is the fraction of g r a i n volume transformed, temperature, and then performing the metallographic
and P is the number of martensitic plates within the measurements r e q u i r e d by Eqs. [1] and [2]. Such val-
grain. Fisher's partitioning formula is adopted h e r e , ues of 5 are summarized in Fig. 12 for an Fe-24Ni-
as in the e a r l i e r model. 3Mn alloy transformed at various reaction t e m p e r a -
Eq. [7 ] can be numerically integrated by taking suf- t u r e s both above and below the nose of the C - c u r v e
ficiently s m a l l time intervals to yield the d e s i r e d ac- ( - 1 2 5 " C). T h e s e r e s u l t s a r e surprising in that the
curacy. LxNg for such time intervals is obtained from mean volume of the martensitic plates depends not
Eq. [5], and then the increments of transformation only on the extent of transformation (partitioning), but
from these g r a i n s in the f i r s t such time interval and also on the r e a c t i o n temperature. Evidently, p a r t i -
in each subsequent one a r e successively added, k e e p - tioning is not just a problem of spatial geometry.
ing t r a c k of the progressive effects of partitioning in More recently, Pati and Cohen~ have attempted to
the different groups of grains. avoid any r e l i a n c e on a partitioning relationship by in-
The foregoing kinetic model, ~ b a s e d on the cluster- corporating the actual 5-determinations, Fig. 12, in
formation of martensite, improves the a g r e e m e n t be- the kinetic treatment. The number of most-potent e m -
tween the calculated and experimental curves, com- bryos ( u t ) existing at any time per unit volume of al-
pared to the case in which the nonuniformity of em- loy is taken, as previously:z5
b r y o distribution a r i s i n g from the autocatalytic p r o c -
nt = (hi + P f - N v ) ( 1 - / )
ess is not considered. In Fig. 11, the transformation
curves calculated (A) by taking the cluster-formation = (ni + f [ P - l / E ] ) ( 1 - f ) [8]
2414-VOLUME 2, SEPTEMBER 1971 METALLURGICAL TRANSACTIONS
 i I ~ I i i L I i
_ i i ' oo O l / ~ o / 7 [ I

6 - u - 8 0 , - 9 0 , -105 '='C
20
o - 115, -125°C c ~ ~ Experimental curves
5 _ x - 1 4 0

a - 1 8 3 , -196°C
15- x-8OoC -
E
L~ 4 c:
O
T
<2_ 3
v
;115, t25 °C ~ / 140 C
I>

%~ '---.o.~.-.~-c " o ~
I ! : ! ~ I I
25 50 75 I O0 125 150 175
I0 20 50 40
T i m e , rain
Mortensite %
F i g . 13--Comparison of experimental transformation c u r v e s
F i g . 12--Mean p l a t e volume (v) as a function of martensitic (Fe-24Ni-3Mn alloy) with t h o s e computed from quantitative
fraction ( f ) at indicated temperatures. 24 metallographic d a t a .24

a n d the r a t e of a c t i v a t i o n of s u c h e m b r y o s p e r unit 25 I I [ t I I

v o l u m e of a l l o y is:
d N v / d t = nt v exp ( - & W a / R T ) [9]
T h e i s o t h e r m a l t r a n s f o r m a t i o n r a t e is s i m p l y : x o
~f5
df _ dNv
- - • v [10]
dt dt
w h e r e v is the v o l u m e p e r m a r t e n s i t i c p l a t e f o r m e d I 0 I ~ P . Ix / u ~ Experimental curves
l ~ t .~ o computed points
a t t i m e t . In the p r e v i o u s k i n e t i c E q s . [4] a n d [7], v /b££ /o z~ -14ooc
has been expressed through the F i s h e r partitioning J.bHx /o o -IZS*c
5 ~ /~ x -,,5~c
f o r m u l a . 27 I n s t e a d , w e now n o t e f r o m E q . [2] t h a t :
df = 5 dNv dO
d---[ ---d-i- + N~--d7 ~ I I I I I I
5 20 I0
25 30 1555
Time, rain
dNVat ( dv ) [11]
F i g . 14--Comparison of experimental transformation c u r v e s
(Fe-24Ni-3Mn alloy) with t h o s e computed from quantitative
a n d by c o m p a r i n g E q s . [10] a n d [ 1 1 ] , w e s e e t h a t : metallographic d a t a .24
d3 25
v = v + Nv dNv [12]

I n a s m u c h a s all t h e q u a n t i t i e s on the r i g h t h a n d s i d e of 20 O/~ Experimental curves

E q . [12] c a n be o b t a i n e d by q u a n t i t a t i v e m e t a l l o g - Of computed po[nts
r a p h y , 2a the F i s h e r p a r t i t i o n i n g a s s u m p t i o n c a n b e r e -
p l a c e d by e x p e r i m e n t a l q u a n t i t i e s , and t h e n : ~15
g
df = ( n i + f [ [ - 1 / ~ 3 ] ) ( 1 - f ) v exp ( - A W a / R T )
dt
d5

F o r e a c h r e a c t i o n t e m p e r a t u r e , ~ is k n o w n a s a /o ° x---
f u n c t i o n of f f r o m F i g . 12, a n d t h e n N v c a n b e ob- ~ 3 x....x....x~x ~x
t a i n e d a s a f u n c t i o n of f t h r o u g h E q . [2]. A c c o r d i n g l y ,
25 50 75 I O0 125 150 175
the d e r i v a t i v e d ~ / d Nv in E q . [11] can a l s o b e e v a l u - T i m e , rain
a t e d , l e a v i n g p a n d A W a a s the only two a d j u s t a b l e F i g . 15--Comparison of experimental transformation c u r v e s
parameters. Using the same curve-fitting p r o c e d u r e (Fe-24Ni-3Mn alloy) with t h o s e computed from quantitative
a s b e f o r e to fix t h e s e p a r a m e t e r s f o r e a c h r e a c t i o n metallographic data. 24
t e m p e r a t u r e , Pati and C o h e n2a o b t a i n e d the r e s u l t s
p l o t t e d in F i g s . 13, 14, and 15 for the e n t i r e r a n g e of
i s o t h e r m a l t r a n s f o r m a t i o n s in t h e i r F e - 2 4 N i - 3 M n d i c a t e s that p a r t i t i o n i n g d o e s o c c u r , t h e e x t e n t d e -
alloy. p e n d s on the r e a c t i o n t e m p e r a t u r e ( i . e . , t h e t e m p e r a -
T h e s e f i n d i n g s e m p h a s i z e that the p r e v i o u s l y ture-dependent morphology p l a y s a significant role),
adopted partitioningformula b e c o m e s highlyinaccurate a n d t h e p l a t e s i z e s do not c h a n g e by o r d e r s o f m a g n i -
a s the t r a n s f o r m a t i o n p r o c e e d s . A l t h o u g h F i g . 12 in- tude a s r e q u i r e d by the F i s h e r f o r m u l a .

METALLURGICAL TRANSACTIONS VOLUME 2 , SEPTEMBER 1971-2415

 I I I I I [p - 1/fi ] i s l a r g e r , w h e n the g r a i n s i z e is l a r g e r .
1.2
1.0- j tion c o n d i t i o n s to m a k e [ p - 1 / / ~ ] ~ 0 . T h i s m e a n s
o8!
"~ 125*c
0.4!- -so /V////"-'s'
o,//./-,..°.
~ I I I I
0.2 0.4 0.6 0.8 1.0
Normolized time ( t f / t l . o )
Fig. 16--Time-normalized transformation curves for (Fe-
24Ni-3Mn alloy) showing the initial s t a g e s of the t r a n s f o r m a -
tion at the indicated temperatures.
A t i m e - n o r m a l i z e d * plot of the i n i t i a l s t a g e s of the
*The time scaleis normalized for present purposes by dividing the actual re-
action time (t) by the time (fl.o) for 1 pct transformation.
t r a n s f o r m a t i o n c u r v e s , F i g s . 13 to 15, is i l l u s t r a t e d
in F i g . 16. T h e c u r v a t u r e of t h e s e n o r m a l i z e d c u r v e s
p a s s e s t h r o u g h a m a x i m u m n e a r the n o s e of the C -
c u r v e , b e c a u s e the c u r v a t u r e d e p e n d s on the f a c t o r
[ p - - 1/v ] in E q . [ 1 1 ] . T h i s i n t e r e s t i n g b e h a v i o r
a r i s e s m a i n l y b e c a u s e of the v a r i a t i o n s in 5 , a s just
d i s c u s s e d . T h e a u t o c a t a l y t i c f a c t o r p is f o u n d to b e
r e l a t i v e l y i n s e n s i t i v e to t e m p e r a t u r e o v e r this
r a n g e .24
GRAIN-SIZE E F F E C T S
F i g . 2 d e m o n s t r a t e s that the r a t e of 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 n c r e a s e s with t h e a u s t e n i t i c g r a i n
s i z e . ' This is the c a s e e v e n when the f i n 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 is h e l d c o n s t a n t .
T h e a u t o c a t a l y t i c p a r a m e t e r p , as o b t a i n e d f r o m
Eq. [4] t h r o u g h c u r v e - f i t t i n g , is f o u n d to b e i n d e p e n d -
ent of the g r a i n s i z e .1 H o w e v e r , ~7 at a n y g i v e n s t a g e
of t r a n s f o r m a t i o n ( f ) is l a r g e r , the l a r g e r t h e g r a i n
s i z e . This i s t r u e w h e t h e r the m a r t e n s i t i c p l a t e s e x -
tend e n t i r e l y a c r o s s the a u s t e n i t i c g r a i n s1 o r not.25
T h e f a c t o r [ p - l / j ] in E q . [13] is u s u a l l y p o s i t i v e ,
a n d c o n t r o l s the o b s e r v e d a c c e l e r a t i o n of the t r a n s -
f o r m a t i o n due to a u t o c a t a l y s i s . U n d e r s u c h c o n d i t i o n s ,
t h e n , the a u t o c a t a l y t i c e f f e c t is g r e a t e r , i . e . ,
P a t i a n d C o h e n'5 a l s o s h o w e d that the a u t o c a t a l y t i c
a c c e l e r a t i o n of 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 c a n b e
e l i m i n a t e d by a d j u s t i n g the g r a i n s i z e a n d t r a n s f o r m a -
that the g e n e r a t i o n of n e w e m b r y o s d u r i n g the r e a c -
tion is just c o u n t e r b a l a n c e d by t h e c o n s u m p t i o n of e m -
b r y o s , a n d the n u m b e r of e m b r y o s p e r unit u n t r a n s -
f o r m e d v o l u m e ( n t / ( 1 - f ) in E q . [8] r e m a i n s s u b s t a n -
t i a l l y c o n s t a n t at h i . I f [p - 1 / ~ ] h a p p e n s to b e n e g a -
t i v e , the n u m b e r o f e m b r y o s p e r unit u n t r a n s f o r m e d
v o l u m e b e c o m e s s m a l l e r with t i m e , and t h e n u c l e a -
tion r a t e t h e n d e c r e a s e s m o n o t o n i c a l l y , c a u s i n g the
t r a n s f o r m a t i o n to c o m e to a h a l t .
ACTIVATION-ENERGY CALCULATIONS
In d e r i v i n g t h e a c t i v a t i o n e n e r g y f o r the i s o t h e r m a l
n u c l e a t i o n o f m a r t e n s i t e , Shih et a l . zs e s t i m a t e d a n
i n i t i a l e m b r y o c o n c e n t r a t i o n of one p e r g r a i n , w h i c h
gave n i = 105 p e r cu c m f o r the a u s t e n i t i c g r a i n s i z e in
t h e i r experiments. Assuming a constant rate of n u c l e -
a t i o n up to t h e f i r s t d e t e c t a b l e a m o u n t o f m a r t e n s i t e
(0.2 p c t ) , t h e y then c a l c u l a t e d the a c t i v a t i o n e n e r g i e s
from the following equations:
= ni v exp (-LXWa/R T ) [14]
0.002 = fVvi Ti [151
w h e r e vi i s the v o l u m e of the f i r s t p l a t e s to f o r m ,
a n d r i is t h e t i m e to p r o d u c e 0.2 pct m a r t e n s i t e .
R a g h a v a n a n d E n t w i s l e ' took n i to b e 107 p e r c u
c m . T h e y n o t e d that the t r a n s f o r m a t i o n c u r v e s m u s t
b e n o n l i n e a r e v e n up to 0.2 pct t r a n s f o r m a t i o n , a n d
m a d e a l l o w a n c e for this on the b a s i s of a u t o c a t a l y s i s .
T h e y a l s o a s s u m e d , a s did Shih et a l . 13 that t h e i n i -
tial p l a t e s w e r e s t o p p e d only by g r a i n a n d twin b o u n d -
aries.
Pati a n d C o h e n15 r e f i n e d t h e a c t i v a t i o n - e n e r g y c a l -
c u l a t i o n s f u r t h e r , a v o i d i n g the a s s u m p t i o n that t h e
p l a t e s i z e is c o n t r o l l e d by g r a i n - b o u n d a r y o r t w i n -
b o u n d a r y b a r r i e r s , and e m p l o y i n g q u a n t i t a t i v e m e t a l -
l o g r a p h y for a m o r e d i r e c t m e a s u r e m e n t of v i . T h e y
a l s o took into a c c o u n t the i n c r e a s e in t h e n u c l e a t i o n
r a t e due to a u t o c a t a l y s i s , a s p r o p o s e d b y R a g h a v a n
and Entwisle.z The results for an Fe-24Ni-3Mn alloy
a r e g i v e n in T a b l e II. T h e a c t i v a t i o n e n e r g i e s l i e in
the r a n g e of 5 , 0 0 0 to 1 5 , 0 0 0 cal p e r m o l e , a n d d e -
c r e a s e m o n o t o n i c a l l y with d e c r e a s i n g r e a c t i o n t e m -
p e r a t u r e . T h e s e v a l u e s d i f f e r by l e s s t h a n 10 pct
f r o m t h o s e p r e v i o u s l y p u b l i s h e d ,z, ,3

Table I1. Activation Energies for Initial Martensitic ACTIVATION-ENERGY DEPENDENCE

Nucleation in an Fe-24Ni-3Mn Alloy (Ref. 15) ON DRIVING FORCE
Reaction Temperature, °C AWa, cal per mole T h e a c t i v a t i o n e n e r g i e s for i s o t h e r m a l - m a r t e n s i t e
- 70 15,600 n u c l e a t i o n in F e - N i - M n a l l o y s is l i n e a r l y r e l a t e d to
- 80 13,800 t h e c h e m i c a l d r i v i n g f o r c e o f the t r a n s f o r m a t i o n . T h i s
- 90 12,600 is i n d i c a t e d in F i g . 17, the e m p i r i c a l r e l a t i o n s h i p
-105 11,500 being:
-115 10,600
-125 9,800 AW a = 1.05 × 10 -22 (Ag) + 3.66 × 10 -'e e r g s / e v e n t
-140 8,800
-150 8,200 [16]
-183 6,400
-196 5,800 In the c a s e of the F e - 2 9 . 2 N i a l l o y ( w i t h l e n t i c u l a r m o r -
p h o l o g y ) , the e q u a t i o n is:

2416-VOLUME 2, SEPTEMBER 1971 METALLURGICAL TRANSACTIONS

 A Gr'~¢c (col/mole)
T a b l e I l l . Calculated MsTemperatures f o r F e . N i A l l o y s
-550 -500-450 -400 -550 -500 -250-200 Compared w i t h ( N o r m a l i z e d ) Experimental V a l u e s
I I I I I I I

-- 15000 Normalized Anisothermal Athermal

Experimental Ms, ° K Ms, ° K
I0 At. Pct Ni M s , °K ( C o o l i n g Rate 5 ° C / r a i n ) ( A Wa = O)
-- 14000
28.4 252 252 202
29.3 226 225 178
9_ - 13000 29.7 214 211 166
30.7 184 170 130
( 30.9 177 161 122
"E 31.7 141 123 90
i - 12000 32.4 110 82 56
32.7 76 60 38
- I 1 0 0 0 -6
E 33.0 33 30 16
@) 33.2 -
if)i 7- - I 0 0 0 0 33.4 - - -
0 o
# 9000 <3
6 - c o m m o n l y f o u n d a t l o w e r n i c k e l l e v e l s in F e - N i a l -
<3 loys.21, 22
- 8000 For comparison with experimental M s d a t a , the
2:5 Ni 3Mn,24N) 3Mn,25Ni 2Mn transformation-start t e m p e r a t u r e s at a n y g i v e n c o o l -
5 - X Pofiond C°hen(15) - 7000
i n g r a t e c a n be e s t i m a t e d f r o m F i g . 18 a s f o l l o w s .
22.4Ni~3.67Mn~_ • • (14)
23.3Ni-3.8 Mn~ ~ntwlsm The fractional t i m e s (&t/to.l) that the s p e c i m e n
s p e n d s at s u c c e s s i v e 1 o C t e m p e r a t u r e i n t e r v a l s a r e
4 - 23.2Ni-3.6 Mn Shihetal!13) 6000
a d d e d . T h e t e m p e r a t u r e at w h i c h this integrated t i m e
I I lO/l i i i I , I I I I I I l i I i I I I- 5000 b e c o m e s u n i t y is t h e n t a k e n a s t h e a n i s o t h e r m a l M s.
-3.5 -3.0 -2.5 -2.0 -I.5 -I.0 For a cooling r a t e of 5°C per m i n . , A t = 0.2 min and
A gT"~ (109ergs/cm 3) t h e a n i s o t h e r m a l M s t u r n s o u t t o be t h e t e m p e r a t u r e
a t w h i c h t o . i ~ 0.5 m i n . T h e v a l u e s t h u s o b t a i n e d a r e
Fig. 1 7 - - M e a s u r e d activation e n e r g i e s for the i s o t h e r m a l
m a r t e n s i t i e transformation in F e - N i - M n a l l o y s a s a function c o m p a r e d in T a b l e I I I w i t h t h o s e d e t e r m i n e d e x p e r i -
of f r e e - e n e r g y change accompanying the transformation. 15 m e n t a l l y 2° a t t h e s a m e c o o l i n g r a t e . T h e c a l c u l a t e d
a n i s o t h e r m a l M s t e m p e r a t u r e s a g r e e r e a s o n a b l y well
& W a = 3.69 × 10 -al ( A g ) + 8.27 × 10 -xa e r g s / e v e n t with t h e experimental v a l u e s , disappearing at exactly
t h e s a m e n i c k e l c o n t e n t (33 a t . p c t . Ni)o
[17]
T a b l e III a l s o l i s t s t h e a t h e r m a l M s t e m p e r a t u r e s
T h e s e l i n e a r relationships are consistent with the w h e r e & Wa g o e s t o z e r o , t h u s g i v i n g t h e i n s u p p r e s s i -
K a u f m a n - C o h e n m o d e l f o r i s o t h e r m a l n u c l e a t i o n of ble M s. O f c o u r s e , t h e a t h e r m a l M s lies b e l o w t h e
p r e e x i s t i n g e m b r y o s , s°, ai anisothermal Ms, the latter b e i n g dependent on the
U s i n g the v a l u e s of the s l o p e and intercept from c o o l i n g r a t e . Due to l i m i t a t i o n s in t h e c o o l i n g r a t e
E q . [17] a n d t h e f r e e - e n e r g y d a t a f o r F e - N i a l l o y s , t h a t c a n be a c h i e v e d i n p r a c t i c e , t h e a n i s o t h e r m a l M s
Raghavan and Cohena have calculated the t i m e for the b e c o m e s virtually i n s u p p r e s s i b l e w h e n & Wa is s u f f i -
i n i t i a l 0.1 p c t t r a n s f o r m a t i o n ( t o . i ) a s a f u n c t i o n o f ciently s m a l l , even though the a t h e r m a l Ms w h e r e
n i c k e l c o n t e n t a n d r e a c t i o n t e m p e r a t u r e , as s h o w n in A W a = 0 i s not a c t u a l l y r e a c h e d .
F i g . 1 8 . O n l y n i c k e l c o n t e n t s a b o v e 29 p c t N i a r e c o n - T h e s e c a l c u l a t i o n s also i n d i c a t e a m e a s u r a b l e iso-
s i d e r e d h e r e b e c a u s e l e n t i c u l a r m o r p h o l o g i e s a r e not t h e r m a l t r a n s f o r m a t i o n r a n g e o f a b o u t 1 0 ° C a t 29 a t .
p c t N i d e c r e a s i n g t o 6 ° C a t 33 a t . p c t N i , a s d e f i n e d
by t h e v e r t i c a l d a s h e d l i n e s i n F i g . 1 8 . Y e t , s u c h a n
I I I I ~ I I
Experimentally i s o t h e r m a l r a n ge h a s not b e e n f o u n d i n a l l o y s w i t h
Observable A t o m i c % Ni
300 tl Range -- m o r e t h a n 29 a t . p c t N i . I n s t e a d , t h e t r a n s f o r m a t i o n
I 29.3 - s e e m s to set in a b r u p t l y in t h e h i g h e r - n i c k e l a l l o y s .
250 29,7_ A s p o i n t e d o u t by M ~ g e e , 2 a s t r o n g a u t o c a t a l y t i c a c -
* 30,7 - tivity may be o b s c u r i n g the isothermal transformation
200 ; in t h e l a t t e r a l l o y s .
/ / / - It is i n t e r e s t i n g t o note t h a t o n l y a t h r e e - f o l d i n -
c r e a s e i n t h e s l o p e a n d i n t e r c e p t t e r m s o f E q s . [16]
a n d [17] i s s u f f i c i e n t t o c h a n g e t h e p r e d o m i n a n t l y i s o -
t h e r m a l C - c u r v e k i n e t i c s o f F e - N i - M n a l l o y sIs t o t h e
e s s e n t i a l l y a t h e r m a l k i n e t i c s o f F e - N i a l l o y s ,m

ISOTHERMAL NUCLEATION AND THE

I I i , , I I L I | KAUFMAN-COHEN M O D E L
-16 -12 -8 -4 0 4 8 12 16 20
log to. I T h e K a u f m a n - C o h e n m o d e ls°, 31 o f a n o b l a t e - s p h e r -
F i g . 18--Time for the i n i t i a l 0.1 pct transformation (t0.1) a s a o i d a l e m b r y o a s s u m e s slip as t h e l a t t i c e - i n v a r i a n t
function of t e m p e r a t u r e a n d n i c k e l content. 3 s h e a r , w h e r e a s i n t e r n a l t w i n n i n g is o p e r a t i v e f o r t h e

METALLURGICAL TRANSACTIONS V O L U M E 2, S E P T E M B E R 1971 2417

l a t t i c e - i n v a r i a n t s h e a r in t h e p r e s e n t a l l o y s , at l e a s t
in t h e e a r l y s t a g e s o f p l a t e f o r m a t i o n . H o w e v e r , n o
m o d e l is available w h i c h i n c o r p o r a t e s t w i n n i n g in t h e
n u c l e a t i o n e n e r g e t i c s , a n d so we a d o p t t h e K a u f m a n -
C o h e n m o d e l f o r our purposes. I n t h i s model, t h e d r i v -
ing s t r e s s o n t h e interface must n o t only o v e r c o m e t h e
restraining s t r e s s a r i s i n g from the s u r f a c e - e n e r g y
a n d s t r a i n - e n e r g y t e r m s , but m u s t a l s o p r o v i d e f o r
t h e a t h e r m a l creation o f new dislocation l o o p s at t h e
t i p s of t h e e m b r y o s . W h e n t h i s e x c e s s s t r e s s i s not
q u i t e s u f f i c i e n t in m a g n i t u d e , t h e r m a l f l u c t u a t i o n s c a n
b r i d g e the gap. T h e r e s u l t i n g relationship between ac-
tivation e n e r g y for isothermal nucleation (AWa) and
t h e c h e m i c a l d r i v i n g f o r c e (~xg) t u r n s o u t t o b e :
× r ~ ] ergs/event [18]
N o t e t h a t A Wa i s l i n e a r l y d e p e n d e n t o n £xg, i n l i n e
w i t h t h e e x p e r i m e n t a l r e l a t i o n s h i p s i n E q s . [16] a n d
[ 1 7 ] . T h e s t r a i n - e n e r g y p a r a m e t e r ( A ) is u s u a l l y
t a k e n a s 2.1 × 101° e r g s p e r c u c m . E q s . [17] a n d [18]
t h e n g i v e 4202k f o r t h e e m b r y o r a d i u s ( r e ) i n t h e
F e - N i a l l o y s a n d 110 e r g s p e r s q c m f o r t h e i n t e r r a -
c i a l e n e r g y (~). T h e c o r r e s p o n d i n g v a l u e s f o r t h e
F e - N i - M n a l l o y s a r e 2 2 0 A a n d 120 e r g s p e r sq c m
r e s p e c t i v e l y . S i n c e r e is probably a m e a s u r e o f t h e
e m b r y o p o t e n c y r a t h e r t h a n i t s a c t u a l s i z e , we s e e
that manganese r e d u c e s the e m b r y o potency when
a d d e d to F e - N i a l l o y s .
A n a t t e m p t is n o w underway t o a d a p t t h e a b o v e nu-
c l e a t i o n m o d e l t o t h e c a s e of a t w i n - d i s l o c a t i o n i n t e r -
f a c e i n s t e a d o f a d i s l o c a t i o n - l o o p i n t e r f a c e , 3°, 31 t h u s
simulating the internally-twinned martensites in-
v o l v e d in t h e s e i s o t h e r m a l t r a n s f o r m a t i o n s o f F e - N i
and F e - N i - M n alloys. T h e preliminary indications
a r e that the a b o v e v a l u e s for the e m b r y o s i z e s and
i n t e r r a c i a l e n e r g i e s w i l l not be c h a n g e d i n o r d e r of
m a g n i t u d e by t h e s e f u r t h e r r e f i n e m e n t s i n t h e c a l c u -
lations.
C O N C L US IONS
1) Isothermal martensitic transformations in the
bulk can be affected by preferential surface nuclea-
tion. Accordingly, the latter must be avoided in order
to measure nucleation kinetics characteristic of the
volume.
2) The isothermal transformation rate increases
initially due to autocatalysis, whereas the subsequent
decrease in the transformation rate can be attributed
to t h e p a r t i t i o n i n g o f t h e u n t r a n s f o r m e d p h a s e .
3) T h e u s u a l p a r t i t i o n i n g f o r m u l a s e r i o u s l y u n d e r -
estimates t h e m e a n p l a t e v o l u m e at m a r t e n s i t e f r a c -
tions g r e a t e r than 0.15.
4) T h e c o m p u t e d t r a n s f o r m a t i o n c u r v e s g e n e r a t e d
by f e e d i n g - i n q u a n t i t a t i v e m e t a l l o g r a p h i c d a t a s h o w
satisfactory overall agreement with the experimental
2418-VOLUME 2 , SEPTEMBER 1971
c u r v e s . T h i s is n o t t h e case w h e n t h e u s u a l p a r t i t i o n -
i n g f o r m u l a is a s s u m e d .
5) T h e a c t i v a t i o n f r e e e n e r g y f o r i s o t h e r m a l n u c l e -
a t i o n is l i n e a r l y d e p e n d e n t o n t h e c h e m i c a l f r e e -
e n e r g y c h a n g e of the anstenite ~ martensite t r a n s f o r -
mation. The s l o p e s and the intercepts of the l i n e a r
equations a r e significantly different b e t w e e n F e - N i - M n
on the one hand and F e - N i a l l o y s on the other. This
d i f f e r e n c e is s u f f i c i e n t t o change t h e p r e d o m i n a n t l y
i s o t h e r m a l C - c u r v e k i n e t i c s in F e - N i - M n a l l o y s t o
t h e essentially a t h e r m a l k i n e t i c s in t h e F e - N i a l l o y s .
6) S u b s t i t u t i o n o f t h e e m p i r i c a l l y - d e t e r m i n e d p a -
r a m e t e r s into t h e K a u f m a n - C o h e n e q u a t i o n f o r i s o -
t h e r m a l nucleation of preexisting e m b r y o s indicates
t h a t t h e e m b r y o s in F e - N i a l l o y s a r e m o r e p o t e n t t h a n
t h o s e in F e - N i - M n a l l o y s .
ACKNOWLEDGMENTS
This work w a s c a r r i e d out a s a part o f a r e s e a r c h
p r o g r a m a t M . I . T . , s p o n s o r e d by t h e O f f i c e o f N a v a l
R e s e a r c h . V e r y helpful d i s c u s s i o n s w e r e held with
D r s . L . K a u f m a n a n d S. R . P a t i .
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METALLURGICAL TRANSACTIONS