CLASSICAL AND NONCLASSICAL MECHANISMS

OF MARTENSITIC TRANSFORMATIONS
G. Olson, M. Cohen

To cite this version:

G. Olson, M. Cohen. CLASSICAL AND NONCLASSICAL MECHANISMS OF MARTEN-
SITIC TRANSFORMATIONS. Journal de Physique Colloques, 1982, 43 (C4), pp.C4-75-C4-88.
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 JOURNAL DE PHYSIQUE
Colloque C4, suppl6ment au n o 12, Tome 43, d6cembre 1982 page C4-75

CLASSICAL AND NONCLASSICAL MECHANISMS OF MARTENSITIC TRANSFORMATIONS

G.B. O l s o n a n d M. Cohen

MIT, Cambridge, MA, U.S. A.

( A c c e p t e d 9 August 1982)

Abstract. - Theoretical approaches t o the nucleation of martensi t i c

transformations have considered two types of nucleation paths: ( a ) the
classical path, involving a nucleus of fixed structure and increasing
s i z e , and (b) nonclassical paths, involving a nucleus of varying structure.
A unified approach i s out1 ined which allows f o r the theoretical treatment
of homogeneous and heterogeneous nucleation of coherent and semicoherent
martensitic transformations by both types of nucleation paths, and ident-
i f i e s the circumstances favoring each. Nonclassical paths would be favored
in the special case of homogeneous coherent nucleation near a mechanical
i nstabi 1i ty; however, quantitative treatment requires further know1 edge
of the energetics of homogeneous l a t t i c e deformations and the s t r a i n -
gradient energies which control diffuse interfaces. Heterogeneous
nucleation, which governs martensitic transformations i n bulk materials,
favors t h e classical path and involves r e l a t i v e l y sharp interfaces.
Classical heterogeneous nucleation i s adequate1 y treated by 1i near-el a s t i c
continuum and dislocation descriptions. Defect-nucleus interaction leads
to "barrierless" nucleation with kinetics controlled by i n t e r f a c i a l motion.
Details requiring further a t t e n t i o n are the microscopic mechanisms of
martensitic i n t e r f a c i a l motion i n d i s c r e t e c r y s t a l s , and the precise nature
of the nucleating defects, both those i n i t i a l l y present and autocatalytic-
a1 l y generated.

Introduction.- Martensitic transformations have been defined as a subset of

diffusionless displacive phase transformations, with s u f f i c i e n t l y large l a t t i c e -
d i s t o r t i v e shear displacements such t h a t the transformation kinetics and morpho-
logy a r e dominated by s t r a i n energy ( 1 ) . I t then follows t h a t martensitic trans-
formations a r e f i r s t - o r d e r solid-state reactions occurring by nucleation and growth.
While the growth stage of f i r s t - o r d e r transformations generally takes place
by the motion of interfaces which convert the parent phase t o the fully-formed
transformation product, two types of paths have been considered f o r the case of
nucleation. The "classical " nucleation path, analogous t o the growth stage,
involves a nucleus of the same s t r u c t u r e and/or composition as the f u l l y - f o y e d
product, increasing in s i z e by the motion of i t s interface. A "nonclassical
path involves a continuous change in structure/and/or composition in a f i n i t e
region. The two types of paths are i l l u s t r a t e d in Figure 1 where composition,
s t r u c t u r e , and s i z e a r e denoted by C, rl, and n. Path "a" depicts the classical path,
while paths "b" and "c" represent nonclassical paths. For the simple case of
purely compositional transformations, nucleation via nonclassical paths has been
treated quantitatively by Cahn and Hill iard ( 2 ) .
The current s t a t u s of the theory of martensitic nucleation by both classical
and nonclassical paths has been recently reviewed ( 3 ) . While the theory of
nucleation via classical paths i s now well -developed f o r both homogeneous and
heterogeneous martensitic nucleation, speculation regarding the possible re1 evance

Article published online by EDP Sciences and available at http://dx.doi.org/10.1051/jphyscol:1982405

 JOURNAL DE PHYSIQUE

S~ze

Composition, --_____
-. :b
structure
'\ I

IIL)

Figure 1 Classical and nonclassical Figure 2 Free energy per u n i t volume,

nucleation paths f o r f i r s t - o r d e r sol id- Ag, associated with homogeneous distor-
s t a t e phase transformations. Diffusion- tion of the metastable parent l a t t i c e
l e s s martensitic transformation involves (n=0) t o produce the martensitic product
variables 0 ( s t r u c t u r e ) and n ( s i z e ) . (n=1) under thermodynamic conditions
corresponding t o To, Ms, and the
" i n s t a b i l i t y temperature" Ti.
of nonclassical nucleation paths has not y e t evolved a quantitative theory. We
here outline a unified approach t o the quantitative treatment of martensitic
nucleation, which a1 lows f o r both classical and nonclassical paths, and identi-
f i e s t h e circumstances under which each mode of behavior will prevail.
Lattice-Deformation Energetics.- O f importance t o both the energy of a nonclassical
nucleus and the i n t e r f a c i a l energy of a classical nucleus are the energetics of
intermediate configurations i n t h e l a t t i c e deformation of the martensitic trans-
formation. The f ree-energy change per unit volume, Ag , accompanying homogeneous
d i s t o r t i o n of the parent phase to t h e product s t r u c t u r e along a deformation path
(defined by the s t r u c t u r a l parameter n ) i s depicted in Figure 2, with n=0 and rl=l
representing the parent and product structures. The value of Ag a t n=1 corresponds
to the chemical free-energy change of the transformation, dgch, and the maximum in
the curve represents a "homogeneous l a t t i c e deformation barrier" of height 4.
When ngch=O (as indicated f o r the temperatu e T-TO), the b a r r i e r i s designated @,.
When ngch<O, i s l e s s than 4,; and f o r Agc6 su;flciently negative, the condition
@=0, can ( i n principle) be reached whereby the parent l a t t i c e becomes mechanically
unstable as i l l u s t r a t e d f o r an " i n s t a b i l i t y temperature", T=Tj, in Figure 2. While
some transforming materials show an anornolous temperature dependence of e l a s t i c
constants such t h a t a shear constant extrapolates to zero a t a f i n i t e Ti tempera-
ture (4), many systems do not exhibit such anomolies and then a T - temperature
does not exist. As discussed in ref. 3, however, any metastable l a t t i c e can be-
come unstable i f the thermodynamic driving force i s made s u f f i c i e n t l y large, as
f o r example by the application of s t r e s s . As indicated by the curve f o r T=Ms
in Figure 2, martensitic transformations in bulk materials typical1 y nucleate
under thermodynamic driving forces which are f a r removed from the conditions f o r
general mechanical i n s t a b i l i t y of the parent l a t t i c e .
Recent progress has been made i n t h e quantitative estimation of the energy
curves represented by Figure 2, based on higher-order e l a s t i c constants (5,6),
interatomic potentials ( 7 ) , and electronic calculations (8-11 ). The barrier
height 4 i s sensitive t o the nature of the l a t t i c e deformation path. Paths
examined so f a r include "proportional s t r a i n " paths along intermediate configur-
ations defined by the deformation $3, where B i s the t o t a l deformation r e l a t i n g
parent and product l a t t i c e s , and "sequential shear" paths involving close-packed
shear systems as proposed by Bogers and Burgers (12). Calculations to-date suggest
 lower b a r r i e r s f o r proportional s t r a i n paths, with (I
values
, as low as 102 t o lo3
J/mole f o r FCCraCC transformations. The lower b a r r i e r f o r t h e proportional
s t r a i n path compared t o t h e sequential shear paths complicates the i n t e r r e l a t i o n
of thermodynamic s t a b i l i t y (Agch) and t h e behavior of second-order e l a s t i c shear
constants, such as C'=1/2 (Cll-C12) in BCC alloys. Analysis of load-path bi-
furcations during homogeneous l a t t i c e deformation, as studied by Milstein and
Farber ( 7 ) , may c l a r i f y t h i s matter.

The energetic calculations suggest t h a t ~ g ( q )can be reasonably approximated

by a fourth-order Landau expansion:
2 3
Ag = Aq -Bo +Crl
4 , (1 1
where the coefficients A , B , and C are related t o the second, t h i r d , and fourth
order e l a s t i c constants of the parent phase. The dependence of Ag on thermodynamic
conditions can be approximated by expressing these coefficients as functions of
Agch constrained t o give local minima a t r1=0 and q=1. The simplest approxima-
t i o n , which i s most appropriate near a mechanical i n s t a b i l i t y , i s t o take the coef-
f i c i e n t A (controlling mechanical s t a b i l i t y of the parent l a t t i c e ) as a l i n e a r
function of ~ g c h . This gives expressions of the form:

where ACJ?~ i s the c r i t i c a l Agch f o r i n s t a b i l i t y . The l a t t e r can be estimated

from the c r i t i c a l driving force f o r i n s t a b i l i t y under s t r e s s a t T , giving B=
-3.08 ( 3 ) . Energies normalized t o bo can then be simply expresse8 as functions
of t h e dimensionless parameter a , where a=O corresponds t o equal f r e e energies
of the parent and product phases ( A ~ c ~ =and o ) %=I represents mechanical i n s t a b i l i t y
of the parent phase.
Coherent Interfacial/Gradient Energy.- As discussed in r e f . 3, and a l s o developed
by Roitburd (1 3,14), the lower energy of intermediate configurations accompanying
the reduction of $ near a mechanical i n s t a b i l i t y will promote diffuseness of a
coherent martensitic interface. The behavior of t h e i n t e r f a c e i s then best
described by adopting a gradient-energy formulation similar t o t h a t o r i g i n a l l y
applied t o d i f f u s e i n t e r f a c e s in diffusional (compositional ) transformations by
Cahn and H i l l i a r d (15). The volume and surface energy terms of a c l a s s i c a l
description a r e then replaced by a functional of the form:

where K. i s a gradient-energy c o e f f i c i e n t and Ag i s the local free-energy density:

When the i n t e r f a c e i s the invariant plane of an invariant-plane s t r a i n ( I P S )
l a t t i c e deformation, Ag corresponds t o the function of Figure 2 and equation 1 .
For a non-IPS coherent interface additional s t r a i n energy a r i s e s from d i s t o r t i o n s
in the i n t e r f a c i a l plane a s required by compatabil i t y of the deformation across the
interface. The gradient energy < ( 0 ~ ) 2 i' s a t t r i b u t a b l e t o an harmonic many- body
interaction (16).

*The simple form adopted f o r equation 3 i s based on the assumption t h a t a l l defor-

mation s t a t e s l i e along the path corresponding t o the variable q. This will be
valid f o r the simple cases considered here. More general cases a r e describable
via the gradients of the complete s t r a i n tensor (1 3,14).
C4-78 JOUKNAI. I)E PHYSIQUE

Adopting t h e approximation t h a t K i s independent o f n (and n e g l e c t i n g

gradient-energy t e n s o f h i g h e r power than ( v Q ) ~ ) we , can e s t i m a t e a v a l u e f o r r
from knowlege of t h e coherent s u r f a c e energy a t T0(3). For a f l a t coherent I P S
i n t e r f a c e i n the z=O plane, t h e s u r f a c e energy i s :
m

uo =f[ng x
i (J-I-)~] dz , (4)
-03

S o l v i n g t h e E u l e r equation f o r t h e v a r i a t i o n n ( x ) which minimizes a, and assuming

Ag i s o f t h e form o f e q u a t i o n 1, a s o l u t i o n f o r a. i s o b t a i n e d ( 3 ) which i d e n t i f i e s
K as:

and g i v e s an i n t e r f a c i a l w i d t h o f :

For
2
values o f a few mJ/m ( t y p i c a l f o r coherent i n t e r f a c e s ) , t h estimated 9,
values discussed e a r l i e r g i v e d = 10-12 - l ~ J l ~ / m with a hoof 1.
a few By f i t t i n g
: r t o t h e i n t e r f a c i a l behavior a t T , t h e gradient-energy f o r m u l a t i o n w i l l account
f o r b o t h t h e c l a s s i c a l i n t e r f a c e a? a=o and t h e d i f f u s e - i n t e r f a c e behavior a t a = l .

A problem o f r e l e v a n c e t o m a r t e n s i t i c n u c l e a t i o n i s t h a t o f a t h i n s l a b
.
f m a r t e n s i t e centered on t h e z=0 plane where ~ = n T h i s geometry i s i l l u s t r a t e d
n F i g u r e 3. For a coherent I P S p a r t i c l e , t h e t o f a 1 free-energy f u n c t i o n a l o f
i n t e r e s t i s now: ea

Boundary c o n d i t i o n s f o r t h e v a r i a t i o n n ( z ) a r e q(o) = no. q(m) = 0, and nl(m) = 0

w i t h rl'<D f o r z>O. A f i x e d t o t a l displacement across t h e p a r t i c l e corresponds
t o the condition:

90
ndz = IJ (8)

where u i s t h e displacement parameter i d e n t i f i e d i n F i g u r e 3. The l a t t e r c o n d i t i o n

d e f i n e s a f i x e d e f f e c t i v e semithickness o f t h e s l a b expressed as:

c = u/nO (9)

The form o f t h e E u l e r e q u a t i o n f o r d e t e r m i n i n g t h e v a r i a t i o n n ( z ) which minimizes

t h e f u n c t i o n a l FA, e q u a t i o n 7, s u b j e c t t o t h e c o n s t r a i n t o f equation 8 i s :

where A i s a m u l t i p l i e r i n t r o d u c e d by t h e f i x e d displacement c o n s t r a i n t . This

y i e l d s a d i f f e r e n t i a l equation f o r 0 (z) o f the f o n :

(11)
 I Clossicol
heterogeneous
Nonclossicol
homogeneous

F i g u r e 3 Slab o f m a r t e n s i t e centered F i g u r e 4 N u c l e a t i o n b a r r i e r AG* vs a f o r

on z=O plane. C l a s s i c a l p a r t i c l e of
semi thickness 2c w i t h sharp i n t e r f a c e
produces displacement u . y ~ , where yT
i s t h e t r a n s f o r n a t i o n s t r a i n . Dotted
l i n e i l l u s t r a t e s - displacement f i e l d o f
d i f f u s e i n t e r f a c e producing same t o t a l
displacement.
coherent 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 o l i d l i n e s d e p i c t behavior f o r c l a s s i c a l
heterogeneous n u c l e a t i o n f o r v a r i o u s
values o f c/6 corresponding approximately
t o number o f 8 i s l o c a t i o n s i n n u c l e a t i n g
defect. Dashed 1ine represents b a r r i e r
f o r n o n c l a s s i c a l homogeneous n u c l e a t i o n .

For a given nQ, t h e minimum energy v a r i a t i o n f o r n(z) corresponds t o t h e a d d i t i o n a l

boundary c o n d r t i o n q (0)=0, whereby A=-Ago/nO.

S o l u t i o n o f e q u a t i o n 11 f o r n ( z ) as a f u n c t i o n o f q, and h i s g i v e n by the
integration:

S u b s t i t u t i o n o f v a r i a b l e s according t o e q u a t i o n 11 determines FA and u as:

The e f f e c t i v e semithickness c=u/n, can be used t o d e f i n e an i n t e r f a c i a l energy:

These r e l a t i o n s p r o v i d e t h e b a s i s f o r a t r e a t m e n t o f t h e energy o f a m a r t e n s i t i c
nucleus, which a l l o w s f o r b o t h c l a s s i c a l and n o n c l a s s i c a l n u c l e a t i o n paths.

Coherent Nucleation.- The m a j o r c o n t r i b u t i o n t o t h e i n t e r f a c i a l energy o f a t h i n -

p l a t e I P S p a r t i c l e a r i s e s from i t s broad i n t e r f a c e s as opposed t o t h e p l a t e
p e r i p h e r y , w h i l e t h e e l a s t i c energy accommodating t h e t r a n s f o r m a t i o n s t r a i n
r e s i d e s p r i m a r i l y i n t h e r e g i o n of t h e m a t r i x beyond t h e p e r i p h e r y . A c c o r d i n g l y
C4-80 JOURXAT, DE PHYSIQUE

t h e t o t a l energy o f a t h i n - p l a t e nucleus o f r a d i u s r, l y i n g i n t h e z=O plane,

can be reasonably approximated by t h e energy o f a one-dimensional v a r i a t i o n n ( z )
w i t h i n a c y l i n d e r o f r a d i u s r combined w i t h t h e e l a s t i c energy associated w i t h t h e
long-range s t r a i n f i e l d o f a p a r t i c l e o f semi t h i c k n e s s c producing t h e n e t d i s p l a c e -
ment d e f i n e d by u. T h i s approximation w i l l f i t b e s t when t h e i n t e r f a c i a l w i d t h
6 i s much l e s s than r. R e l a t i n g t h e m a t r i x e l a s t i c constants t o t h e c o e f f i c i e n t A
i n e q u a t i o n 1, t h e nucleus energy can then be expressed by:

where 5 i s an accomnodation f a c t o r equal t o w(2-v)/4(1-v) f o r t h e case o f a simple

shear. The f u n c t i o n s FA and u can be evaluated from e q u a t i o m 13 and 14 u s i n g
equations 1 a ~ 2d t o express Ag. The a c t i v a t i o n energy f o r homogeneous coherfnt, ,
n u c l e a t i o n AG can t h a n be e v a l u a t e d from a saddle p o i n t o f AG ( r , n , A ) a t ( r ,n,,X )
corresponding t o a maximum of AC w i t h r e s p e c t t o r and a minimum w i t h r e s p e c t t o
Q and A. The c o e f f i c i e n t s of equations 2 and 7 a r e most c o n v e n i e n t l y f i t t e d t o
tRe c l a s s i c a l i n t e r f a c i a l parameters a t a=O by n o r m a l i z i n g energies ( p e r volume)
w i t h r e s p e c t t o @, and distances w i t h r e s p e c t t o 6, (equation 6 ) .

I n s p e c t i o n o f these equations r e v e a l s c e r t a i n f e a t u r e s o f a coherent nucleus

which p a r a l l e l t h e C a h n - H i l l i a r d d i f f u s i o n a l n u c l e a t i o n b e h a v i o r as discussed i n
r e f . 3. Since FA must be n e g a t i v e f o r a c r i t i c a l nucleus, no* must be s u f f i c i e n t l y
l a r g e t h a t Ago<O. As i n d i c a t e d by F i g u r e 2, t h i s c o n d i t i o n i s met by p r o g r e s s i v e l y
s m a l l e r n as w 1 . While a c r i t i c a l nucleus a t low a w i l l r e q u i r e n o = l and t h e
h i g h energies o f i n t e r m e d i a t e c o n f i g u r a t i o n s w i l l cause t h e i n t e r f a c e t o remain
f a i r l y sharp, t h e l o w e r a l l o w a b l e values o f no and lower i n t e r m e d i a t e energies
w i l l promote d i f f u s e i n t e r f a c e s o f lower energy w i t h F A 2 as a = l i s approached.
Since b o t h t e n s o f e q u a t i o n 16 vanish as A 4 a t a = l , AG f o r a n o n c l a s s i c a l
nucleus (n,<l) vanishes a t a = l as d e p i c t e d by t h e dashed l i n e i n F i g u r e 4 t Thus,
w h i l e c l a s s i c a l n u c l e a t i o n t h e o r y g e n e r a l l y p r e d i c t s a AG which i s t o o h i g h f o r
thermal a c t i v a t i o n o f homogeneous n u c l e a t i o n i n most c i r c ~ m s t a n c e s , d e v i a t i o n s
from c l a s s i c a l b e h a v i o r near i n i n s t a b i l i t y can reduce AG enough so t h a t t h e r m a l l y -
a c t i v a t e d homogeneous coherent n u c l e a t i o n w i l l precede t h e a c t u a l i n s t a b i l i t y . T h i s
r e s u l t o b t a i n s f o r t h e simple case o f an IPS l a t t i c e deformation. I t i s n o t
c l e a r t h a t t h e a d d i t i o n a l s t r a i n energy a s s o c i a t e d w i t h i n t e r f a c i a l d i s t o r t i o n s
i n a non-IPS coherent t r a n s f o r m a t i o n w i l l vanish a t a=], b u t i t can be expected
t h a t n o n c l a s s i c a l behavior w i l l g e n e r a l l y a l l o w a s u b s t a n t i a l r e d u c t i o n i n
AG* f o r homogeneous coherent n u c l e a t i o n near a mechanical i n s t a b i l i t y .

I t i s o f course w e l l e s t a b l i s h e d t h a t 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 t y p i c a l l y
n u c l e a t e heterogeneously. The h i g h a l e v e l s necessary f o r homogeneous n u c l e a t i o n
can o n l y be i f nucleation a t imperfections i s eliminated. Theoretical
predictions F7sCt87 and experimental observations (1 9-23) i n d i c a t e t h a t t h e most
comon n u c l e a t i o n s i t e s a r e l i n e a r d e f e c t s which can be modelled as groups o f
d i s l o c a t i o n s . Heterogeneous n u c l e a t i o n o f t h e coherent nucleus considered here
can be modelled by t r e a t i n g i t s i n t e r a c t i o n w i t h t h e s t r e s s f i e l d od o f t h e d e f e c t
i n t h e z=O plane. The i n t e r a c t i o n energy f o r a ribbon-shaped nucleus- o f l e n g t h
L, w i d t h a, and semi t h i c k n e s s c l y i n g along a d e f e c t p a r a l l e l t o t h e y a x i s i s
then :

int - 2 ~ t - r ~ J od-qcdx (17)

r0

* w i t h i n t h e approximation o f e q u a t i o n 16, AG* o f a c l a s s i c a l nucleus (n,=l) also

vanishes as A-O. This a r i s e s from n e g l e c t o f t h e s u r f a c e energy contribution o f
t h e p l a t e p e r i p h e r y . A mqre r e a l i s t i c (nonvanishing) b e h a v i o r o f t h e c l a s s i c a l
GG* near a = l i s o b t a i n e d by adding a 4.i;rco term t o e q u a t i o n 16, w i t h a d e f i n e d
by e q u a t i o n 17. The n o n c l a s s i c a l AG* s t i l l vanishes a t 3=1.
where y~ i s the transformation s t r a i n and ro i s the defect core radius. The
t o t a l nucleation energy change AG can be expressed by combining Ei with the
-
two terms of equation 16 modified f o r the ribbon shape. For a disyocation
defect with a x-1 s t r a i n f i e l d , equation 17 introduces a negative energy
contribution proportional t o In a which substantial 1y reduces AG*, promoting
nucleation a t lower a values.
As equation 17 indicates, the nucleus-defect interaction energy i s propor-
tional to qo and heterogeneous nucleation thus favors classical nucleation, The
range of a required f o r c l a s s i c a l heterogeneous nucleation can be estimated from
a dislocation-dissociation model of heterogeneous nucleation (17) in which nuclei
form a t a constant thickness determined by the number of d i s l o c a t i o m i n the
nucleating defect. The classical b a r r i e r AG* goes abruptly t o zero when the f a u l t
energy associated with the dissociation becomes negative. For the simple coherent
transformation considered here, t h i s occurs a t a c r i t i c a l driving force of
agch = -o,/c. Taking o,=4$66,/3 from equations 5 and 6 , the c r i t i c a l a f o r
nucteation i s then:

The behavior predicted f o r various values of c/6 , corresponding approximately

t o the number of dislocations in the nucleating dgfect, i s shown by the solid
l i n e s in Figure 3. For defects of the s i z e which accounts f o r bulk nucleation
in s t e e l s , % i s of the order of 0.1. In addition to the strong interaction
energy favoring a classical qO=l nucleus, the occurrence of nucleation a t such low
a values will favor sharp interface behavior such t h a t no significant deviation
from a classical nucleation path i s expected f o r heterogeneous coherent nucleation.
To summarize the r e s u l t s depicted in Figure 4, heterogeneous coherent nuclea-
tion a t low a will favor nucleation via the classical path. I f heterogeneous
nucleationcan be suppressed, homogeneous coherent nucleation a t high a will then
favor a nonclassical path and the associated nucleation b a r r i e r i s expected t o
reach a thermally-surmountable level before general l a t t i c e i n s t a b i l i t y can be
reached.
Semicoherent Nucleation.- W i t h the exception of F C C d C P and some BCC+9R
transformations, the 1a t t i c e deformation accompanying most martensi t i c transforma-
tions i s not s u f f i c i e n t l y close to on IPS t o allow f u l l y coherent transformation.
Under the thermodynamic conditions where these transformations a r e known t o occur,
the volume s t r a i n energy associated w i t h d i s t o r t i o n s in a f u l l y coherent interface
would exceed the chemical driving force, and so a martensi t i c p a r t i c l e can only be
s t a b l e in a semicoherent form with sufficient1 y reduced s t r a i n energy.
Semicoherence i s achieved through a l a t t i c e - i n v a r i a n t deformation by s l i p
o r twinning which a l t e r s the net transformation shape s t r a i n , generally toward an
IPS. A necessary consequence of the l a t t i c e - i n v a r i a n t deformation i s a modification
of the i n t e r f a c i a l structure, introducing a short-range i n t e r f a c i a l e l a s t i c s t r a i n
f i e l d (with range comparable to the spacing of the twins o r s l i p dislocations
in the interface) which contributes a substantial increment t o the interfacial
energy. In contrast t o the behavior of f u l l y coherent interfaces just discussed,
the i n t e r f a c i a l energy of a semicoherent p a r t i c l e in an anisotropic crystal will
generally have contributions from e l a s t i c constants which do not vanish a t an
i n s t a b i l i t y . Similarly, nonvanishing e l a s t i c constants will also l i k e l y contribute
t o the accommodation s t r a i n energy associated with the net transformation s t r a i n
(shape change). Thus the intgrfacial energy and s t r a i n energy will remain f i n i t e ,
and the nucleation b a r r i e r AG f o r homogeneous nucleation of a semlcoherent
.
martensitic p a r t i c l e will not vanish a t a=l Nonclassical diffuse-interface
behavior should play only a secondary role in semicoherent martensi t i c nucleation,
as reflected by j u s t a moderate reduction in interfacial energy accompanying a
widening of the cores of i n t e r f a c i a l dislocations. Classical calculations indicate
 JOURNAI. DE I'IIYSIQUE

I
iiz

Figure 5 Schematic i n t e r f a c i a l dislocation structure f o r semicoherent F C C 4 C C

transformation nucleus lying in close-packed (1 11) plane.

that homogeneous nucleation of semicoherent martensitic transformations i s highly

improbable under the thermodynamic conditions where these transformations typic-
a l l y occur (24).
For the case of heterogeneous nucleation, the considerations previously
discussed f o r coherent nucleation combined with the properties of semicoherent
interfaces j u s t described make i t highly unlikely t h a t semicoherent nucleation
will deviate s i g n i f i c a n t l y from the classical nucleation path. The essential
features of heterogeneous c l a s s i c a l nucleation of semicoherent transformations
a t dislocation-like l i n e a r defects a r e now well established, based on both specific
dislocation-dissociation models (17,25,26) and general continuum-elastic calcula-
tions (18,27,28). A general r e s u l t i s t h a t ( a ) AG*f o r heterogeneous nucleation
will vanish a t a r e l a t i v e l y modest (compared t o t h a t f o r a = l ) c r i t i c a l driving force
which depends on the defect s i z e , and (b) the c r i t i c a l condition wi 11 be preceded
by the formation of s t a b l e subcritical classical embryos a t very low driving forces.
The short-rangeinteraction with dislocations i s so strong t h a t the l a t t e r embryos
may e x i s t above To (Agch>O). The prediction of pre-existing classical embryos
and the greater interaction energy f o r c l a s s i c a l vs. nonclassical embryos discussed
e a r l i e r reinforce the conclusion t h a t heterogeneous semicoherent martensitic nuclea-
tion will follow a classical r a t h e r than non-classical nucleation oath.

The detailed behavior of AG*f o r heterogeneous nucleation i s s e n s i t i v e to the

constraints applied t o t h e nucleus. Dislocation-dissociation models f o r heterogeneous
nucleation a r e based upon a discrete-dislocation description of nucleus i n t e r f a c i a l
structure, intended t o r e f l e c t discrete-crystal constraints on the i n t e r f a c i a l
mobility and morphology of a microscopic p a r t i c l e . A s p e c i f i c nucleus model ( 2 5 )
f o r semicoherent FCC+BCC trans formation i s depicted in Figure 5. The transformation
l a t t i c e deformation i s accomplished bya a homogeneols array of coherency dislocations
(29) with approximate Burgers vectors 11211 and [121], each array producing
an IPS on crystal planes of closest (30). A6semicoherent interface i s
obtained by the superpositign of a perigdic array of (anticoherency) s l i p disloca-
tions with Burgers vectors - [TIO] and - [Oll], accomplishing a lattice-invariant
deformatign. The major comaonent of t h i transformation net shape s t r a i n a r i s e s
from the - [I211 coherency dislocations. If the nucleation of individual loops
of these Afs~ocationsi s d i f f i c u l t a t small s i z e s , the habit of a microscopic
p a r t i c l e will be confined to the close-packed (111) plane. A fixed number of the
l a t t e r dislocations can be derived from the dissociation of a group of existing
dislocatiorr, as represented in Figure 6a, allowing formation of a ribbon-shaped
anucleus of width a and thickness 2c. If the d i f f i c u l t y of forming additional
[I211 coherency dislocations i s removed a t l a r g e r p a r t i c l e sizes by an athermal
Xgchanism ( t o be discussed), the kinetics of nucleation will be controlled by the
Figure 6 Geometry o f nucleus and d e f e c t f o r heterogeneous n u c l e a t i o n , d e s c r i b i n g
nacleus as ( a ) d i s c r e t e d i s l o c a t i o n a r r a y , and ( b ) continuum p a r t i c l e .

widening o f t h e nucleus a t c o n s t a n t thickness. As described e a r l i e r f o r t h e case

o f heterogeneous coherent n u c l e a t i o n by d i s s o c i a t i o n t h i s geometric n u c l e a t i o n
p a t h has t h e c h a r a c t e r i s t i c t h a t t h e free-energy b a r r i e r AG* drops a b r u p t l y t o zero
when t h e e f f e c t i v e f a u l t energy accompanying d i s s o c i a t i o n becomes negative.
Widening o f t h e nucleus i s then c o n t r o l l e d by t h e d i s c r e t e - c r y s t a l k i n e t i c
processes governing t h e motion o f t h e a [ I 2 1 1 coherency d i s l o c a t i o n s and t h e
concomitent f o r m a t i o n o f t h e i n t e r f a c l g l d i s l o c a t i o n s o f F i g u r e 5. The thermodynam-
i c c o n d i t i o n s f o r t h e f a u l t energy t o become n e g a t i v e can be expressed as a f u n c t i o n
o f d e f e c t s i z e (as f o r t h e coherent case i n e q u a t i o n 18) v i a c l a s s i c a l n u c l e a t i o n
t h e o r y (1 7,25). By t h i s d i s s o c i a t i o n mechanism, t h e n u c l e a t i o n k i n e t i c s a r e
governed n o t by heterophase f l u c t u a t i o n s surmounting t h e b a r r i e r AG*, b u t r a t h e r
by t h e microscopic processes o f i n t e r f a c i a l motion a t a pre-formed c l a s s i c a l embryo
where AG*=O.

Numerical continuum e l a s t i c c a l c u l a t i o n s by Suezawa and Cook (18) a l s o

p r e d i c t t h a t AG* can vanish f o r heterogeneous c l a s s i c a l n u c l e a t i o n a t a l i n e a r
defect, b u t t h e behavior o f AG* d i f f e r s i n d e t a i l f r o m the above d i s l o c a t i o n -
d i s s o c i a t i o n model due t o d i f f e r e n t c o n s t r a i n t s a p p l i e d t o t h e nucleus; nucleus
t h i c k n e s s i s unconstrained i n t h e Suezawa-Cook treatment, b u t an o b l a t e - s p h e r o i d a l
nucleus shape i s imposed. L i n g and Olson (27) have demonstrated w i t h s i m i l a r
c a l c u l a t i o n s t h a t a ribbon-shaped nucleus has a l o w e r energy than an o b l a t e -
spheriodal nucleus when forming i n t h e s t r a i n f i e l d o f a l i n e a r defect. B a r r i e r -
l e s s n u c l e a t i o n o f a ribbon-shaped p a r t i c l e w i l l o c c u r even when AG* f o r t h e o b l a t e
s p h e r o i d i s s t i l l f i n i t e . These r e s u l t s a r e supported by a simple a n a l y t i c a l
t r e a t m e n t o f t h e problem by R o i t b u r d ( 2 8 ) .

The c a l c u l a t i o n s o f L i n g and Olson (27) demonstrate t h a t t h e d i s c r e t e -

d i s l o c a t i o n and c o n t i n u u m - e l a s t i c nucleus d e s c r i p t i o n s a r e e n e r g e t i c a l l y e q u i v a l e n t

o f a continuum p a r t i c l e w i t h a n e t t r a n s f o m a t i o n s t r a i n ~7.
when i d e n t i c a l c o n s t r a i n t s a r e employed. T h i s was shown b computing t h e energy
equivalent t o that o f
t h e nucleus o f F i g u r e 5 i n t e r a c t i n g w i t h t h e same d e f e c t a s J i n F i g u r e 6. Using
parameters a p p r o p r i a t e t o s t e e l s , the c a l c u l a t e d t o t a l free-energy change p e r
l e n g t h , Ge, vs. nucleus width, a, a r e p l o t t e d i n F i g u r e 7 f o r t h r e e l e v e l s o f
chemical d r i v i n g f o r c e . The curves a r e f o r v a r i o u s f i x e d nucleus thicknesses,
w i t h t h e numbers i n d i c a t i n g the t h i c k n e s s i n number o f c r y s t a l planes. The
d o t t e d curves denoting a t h i c k n e s s o f 15 planes correspond t o a nucleus t h i c k n e s s
equal t o t h e h e i g h t h o f t h e d e f e c t ( F i g u r e 6 ) as adopted i n t h e d i s l o c a t i o n -
d i s s o c i a t i o n d e s c r i p t i o n (25). The computed energies i n c l u d e a s t r a i n - e n e r g y
c o n t r i b u t i o n a r i s i n g from e l a s t i c d i s t o r t i o n s i n the i n t e r f a c e ( h a b i t ) plane
 JOUllNAL DE PHYSIQUE

Figure 7 Total free-energy change per unit nucleus length for heterogeneous
FCC-tBCC nucleation in s t e e l s a t three levels of driving force.
Numbers identify nucleus thickness in terms of crystal close-packed
planes. Shear modulus, u ; FCC l a t t i c e parameter, ao. Dislocation
defect in mixed orientation.
imposed by the constraints of a rational (111) crystal-plane habit. The behavior
of the dotted curves i s identical to thatderived from the dislocation-dissociation
model (15,25).
Comparison of the curves for d i f f e r e n t thicknesses v e r i f i e s t h a t the short-
range interactions favor the formation of a subcritical embryo with a thickness
equal to the defect height a t low driving force, as indicated by the arrow
(a/h=lO) in Figure 7a. Once an embryo of t h i s thickness i s e s t a b l i s h ~ d .the
d i f f i c u l t y of nucleating additional coherency dislocations will constrain the
thickness so t h a t the embryo i s s t i l l subcritical (with a/h=30) under the driving-
force conditions of Figure 7b even though a thicker embryo would be s u p e r c r i t i c a l .
For the conditions of Figure 7c, the embryo i n question becomes supercri t i c a l ,
with a negative f a u l t energy then driving the process of i n t e r f a c i a l motion.
A plausible dislocation pole mechanism f o r embryo thickening has been proposed
based on the intersection with f o r e s t dislocations when the conditions f o r unrestrict-
ed nucleus widening a r e met (26). Once thickening can readily occur, the p a r t i c l e
can adopt a minimum-energy habit and morphology, thereby allowing the attendant
reduction in s t r a i n energy t o accelerate the growth process. In s i t u electron
microscopy observations of heterogeneous nucleation in thennoelastic Au-Cd (19)
indicate a change from the close-packed habit t o the macroscopic habit without
evidence of a pole mechanism. Nucleation of additional coherency dislocations
may in t h i s case be stimulated by the f r e e surfaces of the thin-foil specimen.
The increasing separation of the curves of Figure 7c a t large a s i g n i f i e s an
increasing thickening force which might ultimately drive coherency-dislocation
generation under bulk conditions. However, classical (1i n e a r - e l a s t i c )
dislocation-nucleation calculations have not y e t accounted f o r such a process (26).

Defining the end product of nucleation a s an "operational nucleus", t h e

nucleation kinetic behavior discussed here can bedescribedwithin the framework
of general nucleation theory, adopting a nucleation-rate equation of the form ( 3 ) :

where Ni i s the number of nucleation s i t e s of the i t h type, xi i s the fraction

of these s i t e s occupied ( a t a given i n s t a n t ) by operational nuclei, and Bi i s a
frequency f a c t o r controlling the r a t e a t whish nuclei become operational. In
c l a s s j c a l nucleation, the fraction of s i t e s x occupied by nuclei of operational
s i z e n i s expressed by:
= Z exp ( - & G * / ~ T ) (20)
where Z is a nonequilibrium f a c t o r (expressing the fraction of c r i t i c a l nuclei
which reach ); and AG* i s as previously defined. The frequency factor 8 i s the
r a t e a t which these nuclei a r r i v e a t n , and i s expressed as:

where Qm i s the activation energy control ling motion of the nucleus/matrix

interface and v i s an associated attempt frequency. Tn diffusional transformations,
Qm i s the activation energy f o r atomic diffusion, while f o r martensitic transforma-
tions i t i s the activation energy f o r motion of a g l i s s i l e interface.
The operational nucleus i n martensitic transformations has come to be defined
by the point a t which rapid growth begins, i . e . the condition t h a t leads t o a
macroscopically detectable event (31 ) . The strong defect/nucleus interaction
i n heterogeneous martens i t i c nucleation indicates that operational nucleation wi 11
occur under the condition AG*=O whereby the nucleation kinetics (equation 19)
C4-86 JOURNAL U E PHYSIQUE

a r e controlled e n t i r e l y by i n t e r f a c i a l motion. Further progress i n our understand-

ing of the kinetics of martensitic nucleation requires b e t t e r knowledge of the
microscopic processes of i n t e r f a c i a l motion subject to the constraints of the
discrete crystal.
The kinetics of nucleus-interfacial motion have been modelled in terms of
the generation of dislocations producing the lattice-invariant deformation (24,32)
and the motion of coherency dislocations producing the l a t t i c e deformation (26).
Either mechanism can account f o r the experimental nucleation kinetics which show
a l i n e a r dependance of activation energy on driving force. As discussed in
reference 3, no attempt t o account f o r t h i s behavior in terms of a smoothly changing
AG (as opposed t o Q,) has succeeded so f a r .
Nucleation kinetic experiments on the coherent F C C 4 C P transformation i n
Fe-Ni-Mn a1 loys (33), where the l a t t i c e - i n v a r i a n t deformation i s absent, indicate
the same behavior as does the semicoherent FCC+BCC transformation in the same alloy
system. This finding suggests t h a t r a t e control i s by the l a t t i c e deformation i n
both cases, and favors the coherency dislocation motion model. Recent experiments
on the mobility of macroscopic martensi t i c interfaces in thermoelastic 0 CuAl N i
alloys reveal the same kinetic behavior as thermally-activated dislocation motion
(34).
Analogous t o the classical and nonclassical paths which describe the history
of a nucleus as an e n t i t y , the microscopic fluctuations governing i n t e r f a c i a l
motion of a classical nucleus may be of e i t h e r "heterophase" o r "homophase"
character(3). Hence, a1 though the overall nucleus follows a classical path,
nonclassical diffuse-interface concepts may have some relevance t o the i n t e r f a c i a l
mobil i t y , particularly i f widening of the i n t e r f a c i a l core structure increases
mobility as suggested by estimates of the coherent interface P e i r l s b a r r i e r (14).
The macroscopic i n t e r f a c i a l mobi 1i t y experiments (34) suggest an anomol ous
mobility increase a t low temperatures where e l a s t i c softening e f f e c t s a r e encounter-
ed.
While observed heterogeneous nucleation s i t e s of low potency possess many
c h a r a c t e r i s t i c s of the nucleation-site models (19,23), the most potent s i t e s
which i n i t i a t e transformation a t the Ms temperature i n s e e l s a r e known t o
be sparsely distributed with a number density of -106 c!fS (one per lOOw grain)
and a r e therefore v i r t u a l l y unobservable. Efforts t o a r t i f i c i a l l y produce
crystallographically well-defined potent s i t e s in pre-strained synthetic Fe30Ni
bicrystals have been hampered by interference from an unusual isothermal
autocatalytic mode of transformation (formation of paired martensitic units
o r "butterfl i e s " ) which obscures the i n i t i a l events (35). Earlier detection
of i n i t i a l events by acoustic emission measurements might circumvent t h i s
difficulty.
Although autocatalytic nucleation often i n t e r f e r e s with investiyations
directed a t the i n i t i a l nucleation events, the f a c t that the majority of
martensitic units a r e autocatalytically generated makes t h i s an important
phenomenon worthy of study in i t s own right. I t i s c l e a r t h a t the s t r e s s -
a s s i s t e d and strain-induced modes of nucleation which normally account f o r
transformation during deformation wi 11 make an important contribution to
autocatalysis, b u t the autocatalytic nucleation accompanying rapid growth events
in "bursting" alloys i s suggestive of an overdriven process f o r which classical
nucleation kinetic concepts may be inadequate. Autocatalytic nucleation may
represent a f e r t i l e ground f o r exploration of possible nonclassical phenomena.
As a final remark, we have here focussed on nucleation mechanisms f o r
transformations in bulk m ~ t e r i a l s . I t i s well established t h a t f r e e surfaces
can provide a strong stimulating e f f e c t on martensitic nucleation. While i t i s
evident that surface image forces will reduce the s t r a i n energy of a classical
nucleus, a quantitative theory of surface nucleation has not yet been developed.
This i s another area which i s ripe f o r further investigation.
Closure.- T h i s survey o f t h e t h e o r e t i c a l p o s s i b i l i t i e s f o r martensi t i c n u c l e a t i o n
s e t s some d e f i n i t e g u i d e l i n e s f o r t h e circumstances f a v o r i n g c l a s s i c a l and
nonclassical n u c l e a t i o n paths. Nonclassical paths w i l l be favored i n t h e case
o f homogeneous coherent n u c l e a t i o n near a mechanical in s t a b i 1 it y , b u t t h i s wi 11
r e q u i r e t h e suppression of heterogeneous nucleation. This s p e c i a l c o n d i t i o n
might be achieved experimentally i n the case o f small d e f e c t - f r e e metastable
p a r t i c l e s p r e c i p i t a t e d i n a s o l i d m a t r i x , (as i n t h e case o f FCC i r o n i n copper,
o r o f p a r t i a l l y s t a b i l i z e d z i r c o n i a ) which are known t o transform a t q u i t e h i g h
d r i v i n g forces. A more q u a n t i t a t i v e treatment o f nonclassical n u c l e a t i o n would
b e n e f i t from f u r t h e r c a l c u l a t i o n s o f t h e energetics o f homogeneous l a t t i c e
deformations and measurements o f higher-order e l a s t i c constants i n metastable
a1 loys, as w e l l as t h e development o f s t r a i n - g r a d i e n t energies.

The heterogeneous n u c l e a t i o n which c o n t r o l s m a r t e n s i t i c transformations i n

b u l k m a t e r i a l s w i l l f a v o r n u c l e a t i o n by t h e c l a s s i c a l path, p a r t i c u l a r l y i n
semicoherent transformations. I n view o f t h e f a c t t h a t c l a s s i c a l behavior,
i n v o l v i n g r e l a t i v e l y sharp i n t e r f a c e s , i s adequately described by l i n e a r - e l a s t i c
continuum and d i s l o c a t i o n theories, t h e e s s e n t i a l f e a t u r e s o f heterogeneous
m a r t e n s i t i c n u c l e a t i o n a r e considered t o be w e l l understood. Although t h e
d e t a i l e d d i s c r e t e c r y s t a l c o n s t r a i n t s which apply t o a microscopic p a r t i c l e m e r i t
f u r t h e r a t t e n t i o n , t h e o r e t i c a l and experimental evidence p o i n t t o n u c l e a t i o n - r a t e
c o n t r o l by i n t e r f a c i a l motion. Consequently, a b e t t e r understanding o f t h e
mechanism and k i n e t i c s o f heterogeneous m a r t e n s i t i c n u c l e a t i o n r e q u i r e s f u r t h e r
i n v e s t i g a t i o n o f the complete process o f m a r t e n s i t i c i n t e r f a c i a l motion i n a
d i s c r e t e c r y s t a l ; t h i s i n t e r f a c i a l motion may i n w l ve nonclassical phenomena i n
some circumstances .

I s o l a t i o n o f t h e sparsely d i s t r i b u t e d h i g h l y p o t e n t n u c l e a t i o n s i t e s which
i n i t i a t e t r a n s f o r m a t i o n i n the b u l k w i l l r e q u i r e t h e f a b r i c a t i o n o f s y n t h e t i c
n u c l e a t i o n s i t e s i n c a r e f u l l y designed experiments guided by s p e c i f i c s i t e
models. While e x i s t i n g models appear t o reasonably account f o r n u c l e a t i o n i n
deformation-induced transformations, f u r t h e r work i s needed on t h e mechanisms
and k i n e t i c s of a u t o c a t a l y t i c n u c l e a t i o n ( e s p e c i a l l y i n m a t e r i a l s exhi b i t i n g
b u r s t i n g behavior) as w e l l as t h e s p e c i a l case o f m a r t e n s i t i c n u c l e a t i o n a t
f r e e surfaces.

Acknowledgements .-This research i s sponsored by t h e National Science

Foundation under Grant #DMR79-15196. The authors a r e a l s o indebted t o
Dr. H.C. L i n g o f Western E l e c t r i c Engineering Research Labs f o r the e l a s t i c
ca7culations quoted i n F i g u r e 6, and t o Dr. J.W. Cahn o f t h e National Bureau
o f Standards f o r h e l p f u l discussions concerning r n n c l a s s i c a l n u c l e a t i o n behavior.
i o n c l u s i o n s regarding nonclassical behavior near a mechanical i n s t a b i l i t y a r e
based on p r e l i m i n a r y numerical c a l c u l a t i o n s performed by M r . K. B a l l o u as an
undergraduate research p r o j e c t .

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Carnegie-Mellon Univ, P i t t s b u r g , PA (1981) i n press.

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5. CLAPP, P.C., Phys. Status S o l i d i B 57 (1973) 561.

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