]L NUOVO CIMENT0 VOL. 57 B, ~.

2 11 Giugno 1980

A Model for Phase Transition in Pseudoelastic Bodies.

I. Mt+LL~R
~aehbereich 9, Herman~-F6ttinger-Institut, T U Berlin - 1 Berlin 12

]~. ~VILB[A~SKI
Institut o] ~ u n d a m e n t a l Technological t~csearch
Polish Academy o] Sciences - 00049 Warsaw

(ricevuto il 13 Dicembre 1979)

Summary. - - A model ~s proposed which simulates the observed prop-

erties of a pseudoelastic body or meinory alloy. The statistical mechanics
of the model permits the deseriptiotl of the first-order phase transitions
which occur in this alloy. A close analogy between the behaviour of a
pseudoelastic body and a ferroelect~ie body is described.

1. - Introduction.

Pseudoelastie bodies behave much like plastic bodies at low temperatures,

while ~t high temperatures they are elastic. I n particular, such bodies m a y
sustain a residual deformation after a large load has been applied, b u t upon
h e a t i n g the original configuration is restored. Because of this phenomenon
pseudoelastie bodies have been termed bodies with shape memory, or simply
m e m o r y alloys.
Pseudoelastie bodies have also been called ferroelastiq because there is a
certain similarity of their load-deformation curves with the field-magnetization
curves of a ferromagnet. B o t h exhibit a hysteresis, for instance. Actually, the
analogy is m u c h closer and, in fact, striking if we compare the pseudoelastic
behaviour to t h a t of a f e r r o d e c t r i c body. We describe this analogy in sect. 8.
The objective of this paper is the formulation of a model which simulates
the behaviour of a pseudoelastic body. The model consists of a great n u m b e r
of identical mechanical elements which participate in the r a n d o m thermal

283
284 I. l~IOLL]~l% &rid K. WILMANSKI

motion. The elements have two stable equilibrium positions of equal energy
and a metastable one. Statistical mechanics of the model permits the deriva-
tion of explicit functions for the free energy. These functions have a form
characteristic for bodies with a phase transition of the first order and contain
qualitatively most of the properties t h a t are exhibited b y a pseudoelastic body.
Such properties, t h a t are not simulated b y the model, include strain hard-
ening and thermal expansion. This is due to the fact t h a t the model in its
present form does not explicitly consider internal stresses, nor does it take
the expansion of the lattice structure in the body into account.
Also for the present purpose the model has been constructed so as to simu-
late a body under uniaxial tensile or compressive loading. I t will have to be
modified, if we want it to describe more complex loads.

2. - Phenomenology of pseudoelastic bodies.

a) Form o] the state ]unctions.

~) L o a d - d e f o r m a t i o n c u r v e s . The shape of the load-deformation
curve of a pseudoelastic body depends strongly on temperature. This dependence
is illustrated in the schematic figures la) through 1]) which refer to increasing
temperatures. The curves of fig. i are taken from the experimental literature
t h a t is p u t forward in the book (1) edited by PE~:I~S and ill the review papers (2)
b y I)ELAEY, KI%ISHNA~,TAS and WARLIS[O1N~T. ~[n drawing fig. 1 we hay% how-
ever, disregarded the r a n d o m kinks and corners t h a t are usually reported b y
the experimentalists, b u t which we regard as inessential to the physical ex-
planation of the phenomenon of pseudoelasticity.
At low temperatt;res T,, and /~p~ the load-deformation curves arc rcminis-
cent of those of an elastic ideally plastic body. We describe the behaviour
of the body in a de~d-loading experiment. One recognizes in fig. ;In) and b)
a virginal elastic curve at small loads and small deformations and a plastio
yield once the yield load P y is exceeded. P y decreases with increasing tern-
pcrature. I n contrast with the behaviour of a plastic body, there exists a
second elastic branch of the load-deformation curve which occurs at large
deformations and which enables the body to support loads b e y o n d P y . Once
the b o d y has been subjected to a stress greater t h a n P y , it will show a residual
deformation De upon unloading. If we start in the state (P, D ) = (0, Dp)
to compress the body, it will yield at P = - P~ a n d - - u p o n continued com-
pression--it will yield until it reaches the elastic branch in the third quadrant.

(1) J. P~i~KI~S, Editor: Shape Memory Ef]eets in Alloys (New York, N.Y., ~nd
London, 1975).
(2) L. DELA]~Y, R. U. KI~ISENA~, H. TAS and H. WAI~LIMO~T: J. Mat. Sci., 9,
1511 (1974).
A M O D E L F01~ PHASiE T R A N S I T I O N I N _PSEUDO~L~kSTIC ]BODI/~$ ~

The body m a y move up aud down on t h a t branch as indicated b y the arrows.

Unloading now leads to the residual deformation - - D e and subsequent tensile
loading can again cause the body to yield at i~ and to reach the elastic branch
at big positive deformations. I t follows t h a t the b o d y under dead loading
runs through a hysteresis loop around the shaded ~reas fli fig. la) and b).

m f

III /
/ -4~
?Dt'~/;~/t _

r,
D

a) =5
P~_-_: ?_~-]
py___A ~
D
),

--PY =TR,
o)

f /
~A 3

D
)
D

=rq "~-Ts2

Fig. 1.

Moreover, once the b o d y has left the virginal curve, it will not be able, under
dead loading, to assume any state (_P, ])) within the hysteresis loop.
At the higher temperatures TR1 and 2J,~ the load-deformation curve shows
two hysteresis loops under dead loading and these occur in the first and third
quadrant. Figures le) and d) show t h a t there exists an elastic branch at
small loads and small deformations whose slope grows with growing tempera-
ture. Also the yield load P r now increases with temperatttre. Here again the
2~ I. MULLER a n d ~:. ~VILMANSKI

body m a y be loaded b e y o n d the yield load and its states will then be given b y
points on the second elastic branch, along which we m a y move up or dow~l
when we increase or decrease the load. However, unloading will now not lead
to a residual deformation, rather at P -- PR the body recovers what it yielded
at s ~ P y and when P falls below PR the body moves back to the origin along
the initial elastic branch. PR increases with increasing temperature and the
difference between P~ and _P~ grows smaller. Under compressive dead loading
the body behaves like under a tensile load with the obvious differences.
The complete recovery of the initial configuration despite the intermediate
yielding has given rise to the t e r m pseudoelasticity. I t is also said t h a t the
body exhibits shape memory, because, if we leave it at a low temperature Tp~ (say)
in the deformed state (P, D) ~ (0, De), the body will creep back to the initial
shape D -~ 0 when h e a t e d to T.~ (say); this is so because, according to fig. lc)
and d), at the higher t e m p e r a t u r e there is only one possible unloaded state
and this occurs at D ~ 0.
At high temperatures Ts~ and Tz~ the hysteresis loops vanish and we ob-
serve load-deformation curves like those of fig. le) and ]), all parts of which
can be traversed in both directions. In the neighbourhood of the origin the
curve is steeper for a higher temperature.
While in dead loading it is impossible to reach any state within the hysteresis
loop of fig. la) through ld)~ this is well possible if we clamp the body to a de-
formation in the appropriate region. The load that is necessary to maintain
the clamp depends on the m a n n e r in which we apply the clamp~ but, of course,
it is such t h a t the state (P, D) lies within the hysteresis loop. Once such a state
is established, we m a y change it along the dashed elastic lines within the loop
by shifting the clamp.

/~) D e f o r m a t i o n - t e m p e r a t u r e c u r v e s . Another interesting aspect

of a pseudoelastic body is the dependence of the deformation on t e m p e r a t u r e
at a constant load. D a t a for this dependence are less a b u n d a n t in the litera-
ture than load-deformation curves, but some can be found in the papers b y
I%0D]~IGUEZ and BRow~ (see (1), p. 51) and b y B_XU~IGA~T, J0~D~ and ]%EIss (3).
In those reports the thermal expansion is superposed upon the effect typical
for pseudoelastic bodies. If we correct for this, in effect disregarding thermal
expansion~ we obtain a behaviour t h a t is schematically represented in fig. 2.
The curve of fig. 2 was t a k e n from a body under a tensile load. There is a
hysteresis loop in this diagram which corresponds to the hysteresis loop in the
load-deformation diagrams of fig. 1. To permit an easy interpretation, we have
m a r k e d b y A~ through A, the corresponding states in fig. 2 and fig. la), c) and e).
I t is obvious t h a t deformation-temperature curves can be constructed when
load-deformation curves are measured for sufficiently m a n y temperatures.

(3) F. ~BAuMGART, J. JORDE ~nd H. G. R]~ISS: Krupp Forsch. Ber., 34, 1 (1976).
A MODEL FOB, P H A S E TRANSITION IN PSEUDOELASTIC BODIES 287

I n particular, one should then be able to predict the shapes of the deformation-
t e m p e r a t u r e curves for different loads. The m e m o r y p r o p e r t y of the body is
v e r y m a r k e d in fig. 2: the body alternates between large and small deforma-

Fig. 2.

tions as t e m p e r a t u r e Mternates between low and high values. This aspect

of the behaviour of a pseudoelastic body is often called the ~(two-way shape
m e m o r y effect ~).

y) E l a s t i c m o d u l u s . We are not aware of any plots of the elastic

modulus ~t the origin vs. temperature, b u t it seems that, in the range where
fig. la) and b) apply, the elastic modulus decreases with increasing tem-
perature while at higher temperature, where fig. lc) through 1/) apply, the
elastic modulus increases with temperature.

b) Lattice structure.

~) A u s t e n i t e and martensitic t w i n s . There is a l a r g e a m o u n t

of very careful work on the crystallography of the bodies which exhibit pseudo-
elastic effects. Much of it is either reported or referenced in (i). A study of
this literature reveals t h a t there is no single explanation of the effects which
is valid for all pseudoelastic bodies; in fact, the lattice structures m a y differ
widely among such bodies, but, nevertheless, a common feature to all pseudo-
elastic bodies seems to be t h a t a lattice be capable of terra.in peculiar shifts
within a lattice cell.
Indeed, it seems essential for pseudoelasticity t h a t the individuM lattice
cell m a y occur in three different configurations, the p a r e n t configuration and
two identical twins. Figure 3b) shows a two-dimeusionM projection of a face-
centred parent configuration and fig. 3a) and c) show the twins.
Circles and crosses are atoms of the two elements which form the alloy.
The parent configuration is often called austenitic and the twins are marten-
sitic; accordingly we refer to parent and twins as types M+ and M_, respec-
tively, as indicated in fig. 3. The differences in the lattice purameters in the
vertical and horizontal directions of M• are exaggerated in fig. 3, in reality
t h e y usuMly a m o u n t to a few percent at most.
288 I. M I J L L E R and K. ~ILlVIAI~SKI

a) b) c)

Fig. 3.

fi) L a t t i c e d o m a i n s . Of course, the body m a y be built up t h r o u g h o u t

b y lattice cells of only one type. I t m a y be uniformly in austenitic phase as
shown in fig. 4a) or it m a y be uniformly in the martensitie phase of t y p e M+
or M as shown in fig. 4b) and e). B u t in the martensitic phase the body
m a y also assume nonuniform configurations in which certain domMns are
martensitic of t y p e M+ and others are martensitic of type M . A configura-
tion like t h a t is shown in fig. ~d). The dashed lines are the lines of twinning,

~l 9
@
i~
@

/] --
iI ~, M+---
@ @

9 ~ 9

$ $ 9

a) b) c) a)

Fig. 4.

because they separate lattice cells of type M+ from their twins M . The process
of twinning consists of shuffling the a t o m + to a new positive within the
lattice cell and this results in a change of the shape of the cell.
I t is obvious from a comparison of fig. 4b) and c) t h a t the fraction of
twins M+ and M determines the length of the body. I n the present instance,
therefore, a tensile load will promote the formation of M+, while a compressive
load will be favourable for M_. Experiments show t h a t at high temperature
A MODEL FOR PHASE TRANSITION IN PSEUDOELASTIC BODIES 289

the austenitic phase prevails, while at low temperatures we have martensite

either uniformly of types M+ or M or nonuniformly with domains of M+
and M alternating.

3. - Model.

a) Basic element.

g) L a t t i c e l a y e r . I n the definition of the model we are guided b y

the observations t h a t were reported in. the previous section.
As the basic element of the model we, therefore, choose a layered aggTe-
gate of lattice cells, the lattice layer shown in fig. 5 in three different configu-
rations. I n view of subseet. 2 b) we call the configuration in fig. 5b) austenitie

a)

,')~ /]

b) I
i

- - - ~ J I~
c)
Fig. 5.

and denote it b y A, while the configurations of fig. 5a) and c) are called mar-
tensitic and are denoted b y M and M+, respectively. The lattice layer M_
is shorter b y J t h a n A, while M+ is longer b y J. E x c e p t in configuration A
the lattice cells are not rectangular; we accept this drawback of the model
for the sake of simplicity.
We m a y imagine t h a t the three configurations of the lattice layer can be
converted into each other b y applying a shear stress to the top and b o t t o m
surface. I n fact, all intermediate configurations can thus be obtained and
their displacements wili be characterized b y the variable • (see fig. 5b)).
F r e q u e n t l y we shall make this displacement d nondimensional b y choosing
d = A / J as a measure of displacement.
Figure 6a) represents the postulated potential energy r of a lattice layer
as a function of & This potential energy has minima at 8 ---- 0 and 8 ---- • 1.
We conclude from fig. 6a) t h a t the layer configurations in fig'. 5 are equilibria
and, in particular, t h a t the martensitie layers are stable, while the austenitic
one is metastabte. There are energy barriers between the minimal energies
and for IN i > J the potential energy tends to infinity rapidly.

19 - I I N u o v o Uimento B.
290 ~. ~i)LLm~ and x. WIL.~a.~SKI

T h e p o t e n t i a l energy iu the, f o r m s h o w u ill fig. 6{t) was p o s t u l a t e d b y us,

because sueh a p o t e n t i a l will p r o v i d e a t h e o r y t h a t is c a p a b l e of e x p l a i n i n g
t h e load-deform~rtion curves of fig. 1; this is n o t o b v i o u s at lhis stag'e of the
pa.per, nor is it obvious t h a t a t)otential w i t h only the lateral m i n i m ~ al~
d - = :i 1 does not serve the s a m e t)urpose. I l o w e v e r , f r o m our eah.ulations
there is a strong indieation tha.t 1)seudoelast~ieity can only occur if the p a r e n t a l
p h a s e is stable, ,i.e. if q)(._l) has a m i n i n m m at :1 = 0.

q5

>

"-" 0 i 0 1
a) b)
/ % " 9' d2 (3po + 2~v,)64 . (2q% + ~vt) a '; for i,~[ ";: 1 ,
l fro' [,~!> 1 .
Fig. 6.

It would be desirable to derire the f o r m of the p o t e n t i a l enerI~y r from

the d i s t r i b u t i o n of a t o m s ill the lattiee b y t a k i n ~ into a c c o u n t tit(' ~,'an (let
Wa.als forces b e t w e e n tile atorms. But this a p p r o a c h is ditlieull alld r i d d e n
b y u n c e r t a i n a s s u m p t i o n s . Therefore, we prefer lhe s e m i - p h e l m m e n o l o g i e a l
p r o c e d u r e p r e s e n t e d in this paper, which l)roeeeds with a p o s t u l a t e d l)(ttential.

fl) A s i m p l i f i e d p o t e n l , ia.1 f o r the lattiee layer. F i g m ' e 6a)

gives us a q u a l i t a t i v e form of the p o t e n t i a l e n e r g y p o s t u l a t e d for the lattice
layer. But: in the followin~ ealeulations we need a specific function. There-
fore, for p r a e t i e a l pro'poses we shall use the function

q)(S)_= [ 90 I c f , ( ) ~ - - ( 3 q : o - : - 2 ~ v , ) ' 3 ' + ( 2 % - qh) ~> for i ~ , < 1 ,

(3.1)
co/ t'or ,~); > t .

This f u n c t i o n is d r a w n in fig. 6b) for ~0 == 0.3125 and % -- 11.875 al~_d we see

t h a t it has three m i n i m a as r e q u i r e d ; in faet, this f u n c t i o n being s i m p l y
p o l y n o m i , d of order six, in the range bi,,~,l it is tile simplest, f u n e t i o n with
three m i n i m a a.nd t h a t is w h y we ehoose it.

b) l?seudoelastic body.
~) C o n s t r u e l i o n of the body. W e m o d e l the b o d y as a stack
of la.ttiee layers. T h e layers are a r r a n g e d at an angle of 45 degwees to t h e
A MODEL FOR PHASE TRANSITION IN PSEUDOELASTIC BODIES 291

loading surfaces ('). Figures 7a) through 7c) show this a r r a n g e m e n t for the
three cases when the b o d y is either austenitie or martensitie of types M+
and M_ throughout. I t is clear t h a t raider a tensile or a compressive load the
surfaces of the lattice layers are surfaces of m a x i m a l shear stress. Thus the
layers of t y p e A m a y be sheared into layers of t y p e s M+ or M or vice versa
and the configurations shown in fig. 7b) and c) m a y be the result of com-
pressive and tensile loading, respectively.

c~)
S
I / / /
"A
9 A
/
"
A

b) " c)

O
ct)
Fig. 7.

(*) We consider only uniaxial loading in this paper and the model is constructed
accordingly.
292 L M/JLLEI% a~nd_ K. W~LMtkNSKI

B y stacking lattice layers t h a t are either all of type A or of type M_ or of

type M+, we have obtained uniform configurations of the body. If, in the con-
struction of the model, we stack both types of martensitic layers, we obtain
nonuniform bodies of different shapes. Figure 7d) shows this nonuniform ar-
rangement where the lattice layers are alternately of types M+ and M_
with twinning lines separating the two. A little reflection shows t h a t the overall
shape of the martensitic body is determined b y the fraction x of layers of
type M+ (say). I n fig. 7b), c) and d) we havex---- 0, x----1 and x---- 89 re-
spectively.
F o r the most part of this paper we shall be considering uniform bodies
with x either equal to 0 or 1. I n fact, only in sect. 7 will nonuniform configura-
tions with 0 < x < 1 be considered.
The lattice layers will not in general lie still in either one of their equi-
librium positions. R~ther t h e y will perform a r~ndom thermal motion b y
which their length p a r a m e t e r z] is constantly changing and, in general ~t any
given moment, there will not be two layers which have the same value of J .

fl) D e f o r m a t i o n and energy. I n the model, as shown in fig. 7,

the length of the b o d y is defined as the vertical distance of the upper right
and the lower left corner. I n this m a n n e r we make sure t h a t all lattice layers
t h a t contribute to a change of length of the body upon deformation contain
the same n m n b e r of cells. L e t there be N of these lattice layers.
The deformation D of the b o d y is defined as its length minus the length
of the austenitic configuration of fig. 8a). Therefore, we have

(3.2) D = --= ~'3~

~ / 2 i~; '

where A~ is the displucement of the i-th lattice layer. The factor 1/~/2 results
from the arrangement of the layers at an angle of 45 degrees.
The potential energy of the b o d y is assumed to be the sum of the po-
tential energies of the lattice layers (*)

2/
(3.3) E ot = ~ qP(Ai).
i=1

This assumption is probably well justified in the uniform configurations of

the body, where the lattice structure is completely regular. B u t in the case
of nonuniform bodies the additivity of the potential energy m a y be violated,
because the regular lattice structure is disrupted at the twinning line, as shown

(*) We neglect the potential energy of the incomplete layers which do not contribute
to the deformation.
A MODEL FOR PIIhSE TI~,ANSITION IN PSNUDOELASTIC BODIES 293

in the blow-up of p a r t of fig. 7d). Therefore, it is possible t h a t the twinning

lines have a line energy of their own. We neglect t h a t possibility and thus the
nonuniform body of fig. 7d) has the same potential energy as the uniform
bodies of fig. 7b) and e) in the model. This neglect is justified b y a r e m a r k
made b y CAHN (see (4), p. 392).

4. - Statistical m e c h a n i c s o f the m o d e l .

a) Distribution ]unction and expectation values.

~) C a n o n i c a l d i s t r i b u t i o n . Since we assume t h a t the lattice layers

perform a r a n d o m thermal motion, it is appropriate to apply the methods
of statistical mechanics for the determination of the t h e r m o d y n a m i c functions.
Therefore, we consider a canonical ensemble of n identic~i bodies (say) of
deformation D consisting of iV lattice layers. I n a canonical ensemble all these
bodies are supposed to be immersed in a heat b a t h of temperature T. Sta-
tistical mechanics proves t h a t the fraction n ~ j n of bodies with the displace-
ments

is equal to

(4.1) n~l...A~ _ i=I

o [i ]
A1=--co ~/~,=--co i=1

The sttmmation in the exponent extends over all lattice layers, while the sums
in the denominator are sums over all values zJ of each layer. I n all sums proper
regard must be given to the condition t h a t the deformation D is fixed, so t h a t
we have
2g
(4.2) ~: ~ , = V ~ I ) .
i=l

The distribution function (4.1) is called the canonical distribution.

T h r o u g h o u t this paper we ignore the kinetic energy of atoms and lattice
layers. We m a y do so since the kinetic energy of the body will not depend on
the deformation but only on t e m p e r a t u r e and, therefore, it is irrelevant for
the calculation of load-deformation curves and deformation-temperature curves.

(4) R. W. CAIN: Adv. Phys., 3, 363 (1954).

294 I. 3~LrLL3~R a n d K. W l I . M A N S K I

/~) P o t e n t i a l energy. The potential energy of the ensemble is ob-

viously given b y

AI ~-co Zl~v= ~ c o "i=1 " "

N

zJ l = - - - c a ZJN----- co i=l
n

Az =-co AN =-0o i=I

o M /ll

Accordingly the expectation value of potential energy of a single b o d y is given b y

(4.3)

The constraint (4.2) m u s t be t a k e n into account in the evaluation of this ex-

pression. Because of this, the energy of the b o d y is a function of D as well as fT.

7) E n t r o p y . The e n t r o p y of the ensemble is given b y B o l t z m a n n ' s law

k In W ,

where W is the n u m b e r of possibilities, in which t h e n n bodies of the ensemble

can be distributed so t h a t d l , ..., A.v is the set of displacements. I t is well
known that
n!
W=
I] ... fI

holds. W e use the Stirling f o r m u l a for expressing the factorials and obtain
for the e n t r o p y of the ensemble

k In W ~ -- nk ... >~ In .n~l-"zN --

iV

= nk TIn ... exp -

A1=--oo AN=--co

Accordingly the expectation value of the e n t r o p y of a single b o d y of the en-

A MODEL :FOR PIIASE TRANSITION IN PSEUDOELASTIC BODIES 295

semble is given b y

where again (4.2) m u s t be considered, so t h a t it turns out to be a function

of D and T.

6) F r e e energy. The free energy W,ot of a b o d y is defined b y the

equation

Tpot = E~ot-- T H ,
2(

(4.5)

~P~ot is a function of D a n d T, because E ot and H are such functions.

s) P a r t i t i o n function. I n s p e c t i o n of eqs. (4.3)-(4.5) for the ther-

m o d y n a m i c functions E o~, H a n d T~ot shows t h a t all of these quantities ~re
d e t e r m i n e d b y a single function, n a m e l y
~v

which m u s t be calculated subject to the constraint (4.2). I n d e e d we h a v e

In Z (N) ~kT In Z (N)

(4.7) E~o~ = / ~ T 2 - - H -- , T, ot = -- k T I n Z (~') .

T h e function Z (~ is called the partition function of our s y s t e m of ~V elements

a n d its calculation will be the objective of subsect. 4 c). The calculation is some-
w h a t complex and before starting it we need to consider an alternative pro-
cedure in statistical mechanics for the calculation of the t h e r m o d y n a m i c
functions.

b) Alternative calculation o/ thermodynamic /unctions.

I n a b o d y which is built up f r o m m a n y identical and noninteracting elements,
we m a y characterize the state of the b o d y b y giving the fraction N ~ / N of
elements with the displacement zl.
N~ m u s t satisfy the constraints

co co
(4.8) ~ N~ = ~ and ~ /15T~ = V 2 D ,
A=--a~ A=--co
296 I. MULLER and K. WILMANSKI

where (4.8) reflects condition (4.2). The potential energy of the body can be
expressed by the formula
co

(4.9) E o~ =

The e n t r o p y of the b o d y is given b y H = k in W, where

W--

is the n u m b e r of possibilities in which the distribution N~ can be realized.

B y use of Stirling's formula we obtain

~c [ NA.

Thus the free energy }~o~ = E o~-- T H is given b y the equation

o(
=_ N/

and the logarithm of the partition function In Z ( ~ ) = - (P,ot/kT is obtained us

(4.12) in Z(~) - ~ (qS(A) ~__~A)

I t is not easy to calculate Z (~) as a funetion of D and T from this formula 7

because the distribution N~ is unknown. But, if we consider the simple box
potential
0 for [A[ ~< J ,
(4.13) Co(d) = /
t c~ for I d l > J ,

we m a y determine No b y maximizing the e n t r o p y (4.10) under the cm~straints

co co

(4.~4) ~ N~ = iv and ~ AN~ -- ~ / ~ .

A=--m z1=--~

I n this ease N obviously vanishes for [A]> J and we obtain for IA I~<J (*)

(4.15t ~ : N exp [-- (1 + ~)] exp [flAJ,

(*) The subscript 0 refers to the box potential for which q~(A)=0 for IAI<~J.
A MOD:EL F O R P H A S E TRANSITION IN PSEUDO:ELASTIC BODIES 297

where c< and fl are Lagrange multipliers which rosy be determined by inser-
tion of (4.15) into the constraints (4.14). In the determination of the Lagrange
multipliers it is necessary to convert the sums in (4.14) into integrals. There-
fore, we assume t h a t the number of displacements between ~1 and ~1 ~- d3
is equal to zdLJ, where z is some constant of proportionality. All the integrals
can then be evaluated and we obtain 1 ~ g = ]n 2zJ -~ In (sinh fiJ/flJ), so t h a t

o 2 z J sinh flJ exp [-- flA ]

holds. Insertion of this expression for ~ z into (4.14) and calculation of the
integrals leads to ~ relation between the Lagrange multiplier fl and the de-
formation, viz.

(4.17) s = -- ~ 2 ~D- j ,

where Z~f(X) = ctgh ~ / - 1/)/ is the Langevin function. ~ o t e t h a t fi is a one-

to-one function of D.
Insertion of (4.]6) into (4.12) with q ~ ( d ) : qSo(d) leads to an expression
for the partition function appropriate to the simplified problems of the box
potential (4.13), viz.

(4.18) = [=a exp "

The index 0 on -0z(~') indicates t h a t this partition function applies to the box
potential where qs(d) = 0 for ]sJ [ < J . I t is now possible to calculate Epot, H
and [P,ot for this simple potential by use of eqs. (4.7). This leads to the re-
lations
[ --~N2? 1 sinhfiJ]
(4.193 o~OO~=0, q =~Vl~ l n g z J + f i J + n--7~ ] .

Here the index 0 again refers to the box potential ~o(~).

I t is clear t h a t Epot vanishes, because in the box potential the potential
energy of the lattice layers is zero.

c) The partition ]unction and the ]ree energy.

a) P a r t i t i o n function. We return to the potential q~(d) and pro-
ceed to calculate the partition functions (4.6). For this pro'pose we convert
the sums over a]l values of ~, into integrals as before. Thus

(4.20) Z(N)(D'T) = z X "'" ~=lfiexp kT j 6 D ~/~_~ .]dd~ ... d d x

zli=--cO Z]AT~--c~
298 i. ML~LLERand K. WILMANSKI

holds, where the &function under the integral takes care of constraint (4.2). We
recall t h a t ~b(d) is of the form shown in fig. 6b).
The following approximate calculation of the partition function is reminis-
cent of the first step in the virial expansion of the partition function of a real
gas and it was m o t i v a t e d b y t h a t expansion. The calculation proceeds in
four steps.
I n the first step we decompose the exponential in (4.20) additively into
two parts, viz.

(4.21) exp [ - - ~ } ? ] = Fo(A)@ Fl(zJ),

where F 0 is the value of exp [-- r for the box potential,

0 for I A I < J ,
~o(A) = ~ for I A [ > J ,
so t h a t
1 for ]A[ < J ,
(4.22) Fo(A) = 0
for ]A I > J ,
while F~ is the remainder of exp [-- (I)(A)/kTJ, viz.

--1 for IAI < J ,

(4.23) F~(A)= exp[ -~'(71
0 for I A I > J .

Note t h a t I F I ( 3 ) I < 1 holds. Thus the partition function reads

(4.24) Z(~,(D, T) = ~
;/ " ,=1
leI (Fo(d~) + FI(~,)) ~ 1)
( V~l d , )d& ... d ~ , .
--r --co

I n the second step we carry out the multiplication and obtain after some re-
an'angement of terms
co A

9 "

--co --co

(
where Z~v-A'D- (1/V~)E ~, has been introduced for
g=l

= • D 1 1 A
j "~176 / 9 .

--co --co
A MODEL FOR PI-IASE TRANSITION IN PSEUDOELASTIC BODIES 299

Comparison with (4.20) shows t h a t Z-~o (5"--A)(

,-) is the partition function of a s y s t e m
of 2V--A elements subjected to a b o x potential qbo(d ) of the t y p e (4.13);
hence the index 0.
W e h a v e thus succeeded in reducing the cMculation of the partition function
Z ('v) for the potential r to the calculation of the partition functions ~7,(~'-a) 0
for the potential ~b0(3). B u t Z --9
('~'-~) is k n o w n f r o m the considerations of
subsect. 4 b), see (4.18).
I n the third step of the calculation of Z (~" we, therefore, insert (4.18)
into (4.25) and obtain

(4.27) Z(N)(D, T) =
A

ZA ... ,

--co --co

where fl~ is the solution of eq. (4.17) with ~/2D/NJ replaced by

/ A \
b/SD_ A)S. appeudi we pro e that for alues N >> A
i=l

we m a y set fl~ = ft.

This result of appendix A on flA becomes relevant to the determination
of Z (s) in the fourth step, because in the calculation of the sum (4.27) we m a y
restrict the a t t e n t i o n to the lowest values of A. Indeed, since I F d A ) I < I ,
the s u m m a n d s in (4.27) corresponding to higher values of A contribute little
to the s u m and, therefore, it m a k e s little difference whether we use flA or fl
in the summands. F o r the proof of this s t a t e m e n t see appendix B. The limits
of integration m a y be written as =~ J , since FI(A) = 0 for M I > J . We obtain

Z~)(D, T) = Z~)(D) ~ si J2J I(A) exp [ - - r i d ] dA ,

A~O
--J
(4.28)
J

Z('V'(D, T) = Z~')(D) 1 q- s i n h / ~ 2 J FI(zl) exp [--fiA] dd

--J

W e recall t h a t FI(A) = exp [-- qb/kT] - - 1 in the range of integration a n d t h a t

~b(A) is an even function a n d rewrite the square b r a c k e t in (1.28) as

sinh flJ] \2J

--J

W i t h (4.18) we thus arrive at the final f o r m of the partition function for big
~00 I. MU~LLtiil~ and K. WILMANSKI

values of N :
J

(4.29) Z(N)(D,Y) = (2zJ)Nexp [fi~/-2D] 3 I

exp [-- kT-J cosh fiA dLJ)~v.
0

fi) F r e e energy. The free energy ~,ot follows from insertion of (4.29)
into eq. (4.7)3:

(4.30) T~o~(D,T) =
J

;-7,:~ Xln2~J + ~ D +Nln~je~p[--T~- cosh~d~ .

0

We must always recall that ~(fiJ) = -- ~/2D/NJ holds, so that fi is a func-

tion of D.
If the temperature is high enough, we m a y set exp [--~b(~l)/kT] ~ 1 -
-- q~(A)/kT and obtain

(4.31) T,ot(D, 2") =

J

=- ~ [~. +~ ~.NJ J 3r\ ~ -

~~ ~ ~(~)~ ~o~h.
-~T-] d~ 1
o

y) T h e l i m i t qb(A)/kT. If the potential ~(LI) is small compared

to kT, we m a y write

[ q~(A)1 r
kT

and Z (~) in (4.28) m a y be approximated as

J

z(~)(9, T) = zV)(D) [1 - - N 2Jsinhfij

1 /~J
f ~ e x p [ - - ~ A]
dA]
9
--J

The free energy formed with this partitioa function according to (4.7)3 reads

5'

(4.32) U,ot( , T) y ~(~J)exp[--~A]dzl --

sinh fiJ J
--J

- - T { N k ( l n 2 z J + # JTNVJ~-D + an sl--n~Jfi--J)}
'

where we have used the relation in (1 + x) ~ x for x << 1.

A MODEL FOR PHASE TRANSITION IN PSEUDOELASTIC BODIES 301

We understand the status of this limiting expression b e t t e r if we compare

it with subsect. 4 b). Indeed (4.32) is identical to
co

A,d=--m

where ~ o t and H o are energy and entropy for the box potential (see (4.19))
and N00~Jis the distribution function (4.16) of elements in box potentials. Thus
in the limiting case (P(A)<<kT, the free energy ~Ppot= E ~ o t - - T H m a y be
formed with an e n t r o p y calculated for the box potentials and with an energy
t h a t uses distribution functions corresponding to the box potentials.
We have used the limiting form (4.32) of the free energy when we f r s t
presented this research in (5).

5. - Graphical representation o f free energy.

With the potential q~(A) in the form (3.1) the free energy ~P~o~(D,T) of (4.31)
m a y be evaluated graphically and fig. 8 is a graphical representation
of the result for Fo----0.3125 and F 1 - 11.875. The figure shows ~Poj2V%--
--~/Jot(0, s as a function of d - - ~ / 2 ( D / N J ) for 5 typical values of
0 = k T / % (01 = ].21, 0 i i : J , 2 5 , 0 i i I ~ 1.26, 0iv = 1.32, 0v = 1.42).
At a low temperature 0~ the free energy has a m a x i m u m in the origin and
minima on the two sides for positive and negative values of d. At ~n inter-
mediate t e m p e r a t u r e 0 n > 0~ a minimum appears in the origin, while the lateral
minima persist. A somewhat higher t e m p e r a t u r e 0 m makes the minimum in
the origin deeper and the lateral ones shallower. At 0~v > 0H~ the lateral
minimg disappear and we have only the central minimum. B u t at 0~v the
curves ~ vs. D still show two points of inflection both for positive and negative
values of D. I f the t e m p e r a t u r e is still higher, at 0v, the slope of these curves
increases monotonically.
This rather drastic change of character of the (~P, D)-curves occurs in a
fairly narrow range of temperature as can be read off from the numbers in fig. 8.
The dashed parts of the curves correspond to unstable equilibria (D, T),
as we shall see in subsect. 6 a), while the solidly drawn parts represent stable
equilibria. At low temperatures, in the range of 0~, there exist only two such
stable branches, at large negative and positive values of d. These obviously
correspond to equilibria in which the model is in phase M_ or M+, respectively.
In the intermediate t e m p e r a t u r e ranges of 0~, 0 m and 0~v there exist three
stable branches of which the one in the middle represents equilibria in the

(5) I. M?2LLERand K. WILMANSI(I State ]unctions ]or apseudoelastic body, in Proceedings

:

of the Euromech 113, Grenoble, Villard de .Lans (in press).

~02 I. 31(,~LI,Et{ ~111(t K. ~VILMANSKI

aus(.cni(ic phase, whih' (:h(, lateral ones arc m a r t c n s i t i c of lyI)c M_ and M : ,

respcctively. A t high l(,mi)eratur(,s there is no unstable brflllch 1)etw(,en austc-
nitic a n d m a r i c u s i t i c equilibria and, therefore, t h e r e is no ch,ar-(.ut w a y 1o
distinguish those 1)bases. This is akin to (he fact t h a t in a tluid b('yon(1 t h e
critical t e m p e r a t u r e (h(,r(, is no easy distinction b e t w e e n a liquid and a vapour.
The 5 essentially (liff(q.(,n( rang(,s of t('mperaturc, f r o m which 0~ t h r o u g h 0 v
l|)~ve been 1)ickcd are as folh)ws:

O~ < 1.2143)
1.21.13 < 011 < 1.2553 )

(5.~) J .2553 < 01II < 1 .2760 )

1.2760 < ()iv < 1.4195 )

t.-1195 -( 0 v .

The diff('rcnce b e t w e e n the ranlzos I1 a.nd I l l is not easily al)l)reciatcd f r m n the

free-energy curves, b u t it will b e c o m e obvious ill tilt' l o a d - d e f o r m a t i o n curves.
At)art f r o m the 5 t y p i c a l isotherms 0, t h r o u g h 0,-, fig. 8 toni.fins a Sl)ccial
curve corr(,sponding to the I('mpcratur(, 0---1.2.131 for which all three
m i n i m a of the free e n e r g y are equal in del)lh. This curve has a signiii(.ane(,
to be discussed later.

1.0

0.8

0.6
J

I 0.4

).-~ 0.2

-0.2
d
--1
F i g . 8.
A ~ [ 0 D E L F O R 1)HASE T R A N S I T I O N I N F S E U D O E L A S T I C B O D I E S 303

6. - L o a d - d e f o r m a t i o n curves and deformation-temperature curves.

a) Thermodynamic results.

~) G i b b s r e l a t i o n . E n t r o p y H, internal energy E and load P are

all constitutive quantities in t h e r m o d y n a m i c s , i.e. they are related to the
d e f o r m a t i o n D and the t e m p e r a t u r e T in a m a t e r i a l l y dependent manner. But
these constitutive relations are not independent of each other, because be-
tween t h e m the Gibbs equation of t h e r m o s t a t i c s provides the relation

1
(6.1) d H = ~ (dE - - P d D ) .

A little reshufi2ing of terms in the Gibbs equation brings forth an a l t e r n a t i v e

form, n a m e l y the equation

(6.2) d(P ~- -- H d T ~- t) dD

for the differential of the free energy ~ ~ E TH.

H e n c e there follows

~T(D, T)
(6.3) P(D, T) - a_u

and, since E ~ Ski" -[-J~-)~ot contMns the kinetic energy which is i n d e p e n d e n t

of D, we m a y write

~T,o~(D, T)
(6.4) P(D, T) = caD

Therefore, we can obtain the load-deformation curves of our model for dif-
ferent t e m p e r a t u r e s f r o m the ~Vo~ vs. D curves of fig. 8 b y differentiation. The
resulting load-deformation curves are shown in fig. 9 as the solid and dashed
lines for typical t e m p e r a t u r e s in t e m p e r a t u r e ranges 0~ through 0v t h a t were
defined in (5.1). These curves will be discussed in subseet. 6 b) below.

fi) S t a b i l i t y conditions for the uniform body. F r o m the

r e q u i r e m e n t t h a t the e n t r o p y be a m a x i m u m in equilibrium in ,~ b o d y with a.
given energy and deformation t h e r m o d y n a m i c s proves t h a t

(6.5) 8~-~P(D, T ) 0 or 8P(D, T) ~ 0

8D ~ c~D
30~ I. 5I/JLLER a n d K. W I L M A N S K I

must hold, if the pair (D, T) characterizes an equilibrium of a uniform body.

Condition (6.5) is called a t h e r m o d y n a m i c stability condition of such an equi-
librum (D, T).

(7

~) / e)

f"~\\1\\ ~ i
(if" .............
:)
I I I I

. . . .

\\

i o,:1.27
I I
--0.5
I
0
1
0.5
-L J r
--0.5
0n=1.25

0
I i
0.5 --0.5
I

0m=l 2S

0 0.5 --0.5
81~=1.32

0 0.5
I
--0.5
0g =1.42
I
0
I
0.5
I~_

Fig. 9.

Inspection of fig. 8 and 9 shows t h a t parts of the curves ~ v s . D and P vs. D

do not satisfy the stability condition (6.5). Those parts are represented b y the
dashed lines in fig. 8 and 9 and we shall never be able to observe the cor-
responding equilibria in our model.

Y) P h a s e e q u i l i b r i u m . A b o d y m a y sometimes be in a uniform
equilibrium (D, T) which satisfies the t h e r m o d y n a m i c stability condition (6.5)
and y e t it m a y not be in a stable equilibrium. This can happen when the
body is capable of assuming a free energy ~ lower t h a n ~P(D, T) b y decom-
posing into two different phases ~ and fi, thus becoming a nonuniform body.
Phase c~ contributes the part D~ to the deformation D and phase fi contri-
butes D~ such t h a t

(6.6) D = (1 -- x)De, @ xDr

where x is the ratio of lattice layers in phase /3. The free energy is similarly
decomposed into two parts according to

(6.7)

D~ and D~ are uniquely determined b y the condition of mechanical equi-

librium viz.
A M O D E L FOI~ i'I~It$:E T I ~ t N S I T I O N IN PSEUDO:ELASTIC BODI:ES 30~

the load on each phase is the same~

(6.8)1 2(D~, T) = B(Dz, T ) ,

and b y the condition of phase equilibrium, viz.

the free enthalpies of both phases are the same~

(6.8)2 T(D~, T) --.P(D~, T)D~, = T(D~, T ) - - B ( D ~ , T ) D z .

While it is difficult or impossible to find D~ and D~ analytically b y solving

eqs. (6.8), it is easy to construct their values graphically both from the curves
~ ( D , T) and from the curves /~(D, T).
Indeed, b y (6.8)2 and (6.3) the curve T vs. D must have a common tan-

~(D:T)..,/
gent for the deformations D~ and D~; hence their vMues follow, see fig. 10a).

k
P(D~T)

/ 1
I I
i D I

5
Fig. 10.

The slope of the common tangent is the load at which the phases can coexist
at the given temperature. ~
5Ioreover~ from (6.3) we have ~(D2~ T ) - T(1)1; T) :fP(D~ T)4l) for all
Dz
D1 and D2 and, therefore, in particular for D1 - D~ and D~ ~-- D~. Combining
this with (6.8)5, we obtain
DB

P(D~, T)(Z)~- D~) > JP(D, ~) d D .

D~

This means t h a t D~ and D~ are the abscissae of the points of intersect!on of

the curve P(D, T) with the line of constant load which makes the two areas H-
and -- in fig. :0b) equal. This line is called the Maxwell line.
The free energy T ~ of the body in phase equilibrium can be calclflated
from (6.6) through (6.8) to be

(6.9) ~ ----~v(D~, T) @
~T(D~,
~D
T)(D--D~).

~0 - II Nuovo Ciraento B.
306 i. M~LL~R and x. WILMANSKI

These are values on t h e c o m m o n t a n g e n t in D~ and D~ which are lower than

~ ( D , T). Thus, indeed, b y decomposing into two phases tile b o d y assumes a
lower free energy for a given D and T t h a n in the one-phase configuration.

b) Discussion o/ load-de/ormation curves.

~) L o a d - d e f o r m a t i o n curves in dead loading. By (6.4)the
functional relation P(D, T) is obtained f r o m the free energy T~ot(D , T) in (4.30)
upon differentiation with respect to D. We obtain

(6.10) P ( D , T) =

]A exp [-- qb(A )/t~:T] sinh flA dA c~~

=--kT %/2 rid- c%D] ]exp[--~(A)/kT]eosh~AdA 3D}'

0

where, as always, W(~J) ---- -- %/2D/NJ holds. W i t h exp [-- +/kT] ~ 1 -- ~P/I~T
we get

-- kT ( ) ~(1--qb(A)/kT) coshflA dA ~
0
]'

a n d this function is d r a w n in fig. 9 for different values of T. T h e ordinates

in the fig. 9 are a ~ (J/%/2~0)/) and the abscissae are d = %/2DJNJ.
Like the curves T~ot(D, T) of fig. 8, the curves P(D, T) of fig. 9 contain stable
and unstable branches. The latter are represented b y dashed lines. The lateral
solid branches correspond to the stable martensitic phases M_ and M+, while
the central solid branch, when there is one, corresponds to the stable auste-
nitic phase.
F i r s t we discuss the b e h a v i o u r of the model under dead loading at a t e m -
p e r a t u r e in the range 0~v, where fig. 9d) applies.
Application of a tensile load to the u n d e f o r m e d model which is in the
austenitic phase leads to an elastic deformation along the central solid line
and this deformation grows bigger as the load increases. This m a y go on until
the m a x i m u m of the (P, D)-eurve is reached. F r o m there, u p o n the slightest
further loading, the model can only proceed by changing its p h a s e along t h e
dotted line converting ~ustenite into m a r t e n s i t e of t y p e M+. Once the r i g h t
solid line is reached, the whole model is martensitic and it can be further l o a d e d
along this solid b r a n c h or unloaded until this curve has its m i n i m u m . F r o m
-( M O D E L F O R P H A S E TRANSITION IN P S E U D O E L A S T I C BODIES 307

there, u p o n a slight further unloading, the model converts M+ b a c k into austenite

m o v i n g along the lower dotted line until it reaches the central solid b r a n c h
again. Thus we conclude t h a t under dead loading our model correctly describes
w h a t has been observed in pseudoelastic bodies a n d w h a t has been r e p o r t e d
in this p a p e r in subsect. 1 a), fig. Ic) and d). The solid and dotted branches
of the P vs. D graphs enclose a hysteresis region whose points we cannot l'each
b y dead loading.
~ e x t we discuss the b e h a v i o u r of the m o d e l under dead loading a t a tem-
p e r a t u r e in the range 0I, where fig. 9a) applies. H e r e we h a v e no austenitic
b r a n c h a n d we s t a r t the discussion with the unloaded b o d y at d m -- 0.8, where
the model is all in phase M . B y tensile loading we m o v e up the left solid
line until we reach the m a x i m u m . U p o n a further increase of load the model
will convert into phase M~ along the u p p e r dotted line until t h a t reaches the
right solid branch. F r o m here on we m a y f u r t h e r load, or unload, or go into
compressive loading and it seems clear t h a t our model can only surround the
hysteresis region enclosed b y solid and dotted lines, b u t never enter it; a n y w a y
n o t b y dead loading experiments. This betlaviour of the model clearly simulates
the observed hysteresis b e h a v i o u r of a pseudoelastic b o d y at low t e m p e r a t u r e s ,
t h a t was r e p o r t e d in subsect. 2 a), fig. :in) and b).
There is little to say a b o u t the behaviour of the model at a high t e m p e r a t u r e
in the range 0v, where fig. 9e) applies. I n d e e d all parts of the curves can be
t r a v e r s e d in b o t h directions and there is no clear separation of the austenitic
phase for small values of d and of the martensitic phases for large values of d.
H e r e again the model simulates the observed b e h a v i o u r of pseudoelastic bodies
which was discussed in subseet. 2 a), fig. le) and ]).
Figures 9b) and c) exhibit a b e h a v i o u r of the model at t e m p e r a t u r e s in
the ranges 0 H and 0ii I which has not been observed in pseudoelastic bodies to
our knowledge. I n d e e d here the stable austenitic phase exists in the neigh-
bourhood of the origin. F o r 0i~ the austenite is converted into m a r t e n s i t e a t
a load which is smaller t h a n the load for converting the m a r t e n s i t i e phases
into each other a n d for 0 m the inverse is true. This leads to the r a t h e r strange
load-deformation curves of fig. 9b) and c).
W e note t h a t the model can only be m a d e to simulate the hysteresis b e h a v i o u r
of a pseudoelastie body, if we assume t h a t the model does not decompose into
two phases a,nd establish equilibrium between them. This is so because the
t h e r m o d y n a m i c considerations of subseet. 6 a) show t h a t otherwise the load-
d e f o r m a t i o n curves of fig. 9a) and d) (say) would contain Maxwell lines to
replace the hysteresis regions. I n fact, in the ease of fig. 9a) this Maxwell line
would be the p a r t of the d-axis between d ~ -- 0.8 and d ~ + 0.8.
The reason for not having phase equilibrium m a y be t h a t the lattice layers
find it difficult to s u r m o u n t the energy barriers between the different m i n i m a
of the potential-energy curve of fig. 6a). Or else it m a y be t h a t differently
oriented crystallites inhibit each other's motion.
308 L ~0r.LEn and x. WILMANSKI

~) A p h a s e d i a g r a m . The toad-deformation curves d r a w n iafig. 9

are t y p i c a l e~ch for ~ certain range of t e m p e r a t u r % in which qualitatively
similar curves appear. The v a r i a t i o n of shape of these curves within a t e m -
p e r a t u r e range can be read off f r o m fig. :1:1 which presents a phase d i a g r a m

(r I

LO M+

IM_,U§ ~ .

. i I I ; 1 I i I I I I I~
1.21 1.25 1.29 1.33 1.37 1./+1

Fig. 11.

showing regions of the (P, 0)-plane in which we m a y h a v e the phases M_, A

or M+. Quite often two or three phases m a y exist for a given pair P , T and
it depends on the h i s t o r y of the model which one will prevail. The ordinate
of fig. :11 has the same scale as the ordinates of fig. 9.
A t the b o t t o m of fig. :1:1 we h a v e listed the 5 t e m p e r a t u r e regions in which
curves of the 5 different shapes of load-deformation curves appear. I n s p e c t i o n
of the d i a g r a m shows t h a t a decrease of t e m p e r a t u r e in the range 0~ will in-
crease the yield limit. Also the d i a g r a m shows t h a t an increase of t e m p e r a -
ture in the r~nge 0~v will increase b o t h the yield and recovery limits and t h a t
the two limits grow closer together.
All these features of the model simulate the observed features of the pseudo-
elastic b o d y reported in subsect. 2 a), fig. 1.

c) De]ormation-temperatuve curves.
Obviously for the p r e p a r a t i o n of fig. :11 we h a d to h a v e load-deformation
curves for m a n y more temperattlres t h a n the 5 shown in fig. 9. A n d indeed
we calculated such curves for v e r y m a n y t e m p e r a t u r e s over the interesting
i n t e r v a l of t e m p e r a t u r e s . Thus we were also able to construct graphically the
dependence of the deformation on the t e m p e r a t u r e for various prescribed
loads. T h e result is shown in fig. :122 whose curves refer to positive loads
except fig. 12a), which corresponds to zero load. There are various branches
in the d e f o r m a t i o n - t e m p e r a t m . e diagrams of the model which we h a v e denoted
A I~OD~][, }'OR PIiA8~ TRANSITION IN PS~U][)O}gLASTIC BO]DI:NS 309

I I
I I
0.8 a)

0-=0
i i
i I ~ t I t

:x x i
: ~. I
-0.8
I
l
F I
I

I I I
0.8 b)
i lJ-~ z
---0.2
i i i i
I I:
I
i
I
--0.8- I
I
I I
1
i
l I
I c)
0.8- I I
I
I I t :f" u =0.5
r

0 I i : ~I I r ~ i I i i
e._i
-I

-- 0.8-

I
a)
=1.0

o il r i I I I F I I I

,-: ._7

I 1 r i i I I I [. ] ]
1.21 1.25 1 29 L33 1.37 1.41

l~ig. 12.

b y M _ , M+ or A depending on the phase t h a t prevails on these branches.

W e s t a r t with a discussion of fig. 12c). This figure refers to a load of a---- 0.5
and we first consider the ease t h a t a t low t e m p e r a t u r e we find the model to
be uniformly in the phase M+, so t h a t the deformation is positive and fairly
large, d decreases v e r y slowly u p o n an increase of t e m p e r a t u r e until a tran-
~10 L M/.'LLER a n d K. WlL3rANSKI

sition t e m p e r a t u r e 0~+~.A is reached, beyond which the marteusitie phase M+

can no longer exist at the given load. Therefore, the model converts to the
austenitic phase with its ~-ery much smaller deformation. B e y o n d the transi-
tion temperature, the model continues to contract reflecting the growth in
slope of the austenitie load-deformation curves with temperature. A little
reflection shows t h a t the transition t e m p e r a t u r e 0~,• is the temperature in
the region 0,v for which the lower b o u n d a r y of the hysteresis region of fig. 9d)
is equal to the prescribed load. Once we have reached the austenitic phase b y
increasing 0, we m a y go back to the phase M+ when the t e m p e r a t u r e is decreased.
The transition from A to M+ occurs at the transition t e m p e r a t u r e 0A_~,,
which is the t e m p e r a t u r e in the region 0~v for which the upper b o u n d a r y of the
hysteresis region of fig. 9d) is equal to the prescribed load. We thus see t h a t
the hysteresis in the load-deformation diagram leads to a hysteresis in the
deformation-temperature diagram as well, and we conclude t h a t the model is
capable of simulating the observed behaviour of pseudoelastic bodies t h a t was
reported in. subsect. 2 a), see fig. 2. I n particular we see t h a t the model can
simulate the (<two-way shape m e m o r y effect >~ described in subsect. 2 a).
We continue the discussion of fig. 12c) and consider the ease t h a t at low
t e m p e r a t u r e we find the model to be uniformly in the phase M_, so t h a t the
deformation is fairly large and negative,, d increases slowly upon art increase
in t e m p e r a t u r e until a transition temperature 0,s_ is reached whereupon the
deformation jumps to the large positive values of the branch M• The transi-
tion t e m p e r a t u r e 0~_ is the t e m p e r a t u r e in the region 01 for which the left maxi-
mum of the load-deformation curve falls below the prescribed load.
F o r higher loads, for instance ~ = 3.0, the behaviour just described is
qualitatively unchanged, b u t the hysteresis region becomes smaller and the
transition temperatures shift as indicated in fig. 12d).
I n fact, the smaller the load, the smaller are 0~+_~A and 0~_~x+ and the
bigger is 0~_. There comes the point, e.g. when ~ - ~ (t.2, when 0.,i_ > 0~.,~+
holds and in this ease fig. 12b) applies. I f at a low t e m p e r a t u r e we find the
body with a large deformation in phase M+, all is as discussed before. But,
when at a low t e m p e r a t u r e we find the body with a large negative deformation
in phase M_, an increase of t e m p e r a t u r e to 0.~_ will now result in a transition
from phase M_ to phase A.
0v - continues to increase as we apply lower and lower loads and O,~.~ x
eontirmes to decrease until e v e n t u a l l y - - a t ~ - - 0 - - b o t h coincide. The un-
loaded model is a limiting ease in several respects and fig. 12a) applies to it.
If we find the b o d y at large positive or negative deformations, i.e. in phases
M+ or M_ respectively, an increase of 0 will, a.t 0,~_ =- 0,,,+~a, produce a tran-
sition to the austenitie phase with d = O. I t is easy to see t h a t this transi-
tion will take place at the t e m p e r a t u r e 0 ~ 1.2760 which separates the tem-
perature ranges 0 ~ and 0~,.. Once the austenitic phase is thus created, it
will be stable down to the t e m p e r a t u r e 0A~.,z+ ~1.2:143 which separates the
A ~IODEL FOR PHASE TRANSITION ~ IN PSEUDOELASTIC BODIES 311

t e m p e r a t u r e ranges 0, and 0,~. If 0 falls below t h a t temperature, the model

m a y either convert back into M+ o r - - w i t h equal p r o b a b i l i t y - - i t m a y go
into M_. I n d e e d we should expect t h a t half of the model converts into M+
and the other half into M_, thus creating the nonuniform configuration which
we shall discuss in sect. 7 below.
I t remains to discuss the case of v e r y high loads for a > 1.5. H e r e the
hysteresis region vanishes from the deformation-temperature diagram just as,
for high temperature, it vanishes from the load-deformation diagram.

d) Elastic modulus.
The elastic modulus :Y of the model is the slope of the load-deformation
curve at zero load, or the curvature of the free energy-deformation curves at
their minima. B u t there are three minima of free energy in the interesting
range of temperature, namely two identical ones for the martensitie phases M_
and M+ and another one for the austenitie phase A. The corresponding elastic
moduli are drawn in fig. 13. The values t h a t have been used to draw t h a t
figure were calculated numerically from eq. (4.32).

\
" 31

10

8
0
1.21 11.25 1.29 L33
I
1.24-31
Fig. 13.

We conclude from fig. 13 t h a t the elastic modulus of the martensitic phases

decreases with increasing temperature, while the elastic modulus of the austenitie
phase grows as t e m p e r a t u r e grows. This latter observation is also exhibited
b y fig. 9b) through 9e), because these diagrams show t h a t the slopes of the
load-deformation curves of the model increase with increasing 0, which is y e t
another feature in which the model simulates pseudoelastic bodies. W h e n
we start at low t e m p e r a t u r e in the martensitic phase and iucrease the tem-
perature, somewhere the elastic modulus will jump from the branch M+ or M_
312 L M U L L E R and K. W I L M A N S K I

to t h e b r a n c h A. This j u m p in the elastic modulus m a y h a p p e n a n y w h e r e

between 0 = 1.2143, where austenite starts to be stabl% and 0 = 1.2760~ where
m a r t e n s i t e is no longer stable ia the unloaded model. I f we could assume t h a t
during the increase in t e m p e r a t u r e phase equilibrium prevails between m a r t e n -
site and austenite, we should expect the j u m p of Y at 0 = 1.2431, where all
m i n i m a of the free-energy curves lie on the d-axis (see fig. 8). This follows
f r o m the t h e r m o d y n a m i c considerations of sect. 6 as applied to the condition
of zero load.

7. - The n o n u n i f o r m body.

a) Constrained equilibrium.
Figure 10 and the discussion of load-deformation curves of fig. 9 show
w h a t hysteresis means. The b o d y assumes the states on the solid branches of
the free-energy curves r a t h e r t h a n the states on the t a n g e n t where it would
be in phase equilibrium a n d h a v e a smaller free energy.
I n t e r m s of the model the b o d y fails to establish phase equilibrium, be-
cause the lattice layers are constrained in their motion. Two different reasons
can be conceived as possible causes for this constraint:
i) The energy barrier between two equilibrium positions m a y p r e v e n t
the lattice layer to flip to a new equilibrium position.
ii) I n a polycrystalline b o d y the lattice layers will t e n d to inhibit
each other's free motion.

W e are not sure which of these two is the dominating effect~ b u t it seems
t h a t the geometric inhibition described in ii) could be the p r i m a r y reason in
case of the (A~ M+)-transition, while it is primarily the height of the energy
barrier t h a t prevents phase equilibrium between M a n d M+. I n a n y ease
b o t h effects m a y contribute to m a k e the b o d y s t a y in a constrained equilibrium
even though it would stand to gain energy b y the flipping of lattice layers.

b) The constrained equilibria consisting o] M and M+.

W e consider a b o d y in which lattice layers of the types M_ a n d 21/+ coexist
and let x be the fraction of lattice layers of t y p e M+. As ia (6.6) and (6.7)
we thus h a v e

(7.1) D = (1 -- x)D~,_ § xD~+,

(7.2) T~_~+ = ( 1 - - x ) T ( D ~ _ , T) + x~P(D~+, T)

and the condition of mechanical equilibrittm reads as in (6.8)1

(7.3) P(Dz_, T) = t)(D~+, T).

A I ~ O D E L F O R P H A S E T R & N S I T I O N IN P S E U D O E L A S T I C B O D I E S 313

Condition (6.8)2 of phase equilibrium is not satisfied here of course, since we

are dealing with constrained equilibrium.
T(DM_, T) and P ( D ~ , T) are known as the left solid branches of the curves
in fig. 8 and 9 and ~(D~,+, T) and P(Da+, T) are the right solid branches in
those figures. B y use of (7.1) and (7.3), we m a y in principle eliminate D~_
and D~+ from the free energy 5r.~_.,~+ in (7.2) and thus we obtain a function
of D , T and x:

(7.4) T~_~+ = *~'u_~**+(D,T; x).

Holding T and x fixed, we differentiate with respect to D and get

(7.5) P(D, T; ,~) = ~T~_~,§ ~'; x)

c~D

This function determines the load-deformation curve for a given t e m p e r a t u r e

and for a given phase factor x.
The load-deformation curves thus obtained lie inside the hysteresis loop
in fig. 9a) and, in particular, the curve for x = 89 corresponds to the virginal
curve t h a t is observed in pseudoelastic bodies, see subscct. 2 a), fig. a) and lb).
U n f o r t u n a t e l y it is impossible to determine the functions P(D, T; x) ana-
lytically, b u t with some effort one m a y construct t h e m graphically. Using a
slightly different model 5lOLLER (G) and ~.Ii)~ZE~ and VmLAGGI0 C) have drawn
such load-deformation curves of constrained equilibrium.

c) The constrained equilibria consisting of A and M+.

Now we consider a body in which lattice layers of the types A and M+
coexist and let x be the fraction of lattice layers of type M .... This situation
is described b y the same equations as (7.1) through (7.3) b u t with the index M_
replaced b y A. The functions ~Y(D~, T) and _P(D~, T) are known as the solid
branches through the origin of fig. 8 and 9.
J u s t as in the previous paragraph we obtain now

(7.6) P(D, T; x ) =
~D

and this function determines the load-deformation curves t h a t lie inside the
hysteresis loop of fig. 9d). Such curves can be observed in pseudoelastic bodies,
see subsect. 2 a), fig. lc) and d).

(6) I. M~2LLER: Arch. Ration. Mech. Anal., 70, 61 (1979).

(7) I. Mt2nLE~ and P. VIr.LAG~IO: Arch. Ration. Mech. Anal., 65, 25 (1977).
314 i. MULLE:R and K. WILMANSKI

8. - A n a l o g y to f e r r o e l e e t r i c i t y .

a) Phenomenology o/ ferroelectrics.

c~) P o l a r i z a t i o n - f i e l d diagram and polarization-temper-

ature diagram. I n ferroeleetric bodies the dependence of tile polariza-
tion ~ on the electric field E is strongly affected by the temperature. Thus
for three typical temperatures the (z, E)-diagram is shown in fig. 14a) through c).

;Y
b) c)

Fig. 14.

Another aspect of the c o m p o r t m e n t of ferroelectrics reveals itself when

- - a t a constant field--the t e m p e r a t u r e is changed. The resulting polariza-
tions are shown in fig. 15a) through c) which refer to different fields.

T
a) b) c)
Fig. 15.

The curves shown in fig. 14 ~md ]5 are schematized redrawings of meas-

ured curves which are reported, e.g., ill the book b y BU~:~OOT (s).

fl) A n a l o g y of pseudoelastie bodies. Comparison of fig. 14

and 15 in ferroelectries with the load-deformation diagrams and with the
deformation-temperature diagrams of a pseudoelastic body shows a striking
analogy.
The ~nalogy must be drawn b y repla.cing load b y field, deformation b y
polarization and elastic modulus Y by dielectric stiffness S =---~E/~I~= o as
shown in the following small table:

(s) J. C. BURFOOT: Ferroelectrics, An Introduction to the Physical Principles (London,

1967).
A MODEL FOR FIfASE TRANSITION IN rSEUDOELASTIC BODIES 315

Pseudoelasticity Ferroelectrieity
P E
D
Y S

b) Landau's theory o] ]crroelectrics.

~) P o l y n o m i a l representation of f r e e e n e r g y . LANDAU has
o b s e r v e d t h a t the simplest free energy which contains the t h e r m o d y n a m i c
properties of ferroelectrics is a sixth-order polynomial of n of the f o r m (*)

(8.1) ~" = ~o + 89 ~ + I~' + ~n".

H e r e ~ m u s t be negative, ~ m u s t be positive and Z m u s t be a monotonically
increasing function of t e m p e r a t u r e which assumes the value zero at some T = :To.
I n d e e d the graphical r e p r e s e n t a t i o n of the free energy (8.1) leads to curves
as those shown in fig. 16. I n the m a i n qualitative features these curves are

T~-'~(o,T)

y'2
Fig. 16.

similar to those of fig. 8 for the model of a pseudoelastie b o d y and this similarity
is the reason of the a b o v e - m e n t i o n e d analogy between ferroelectricity and
pseudoelastieity.
Once we k n o w the curves ~/J = ~ ( ~ , ~'), all other information a b o u t the
t h e r m o d y n a m i c b e h a v i o u r of ferroelectrics follows just as the t h e r m o d y n a m i c
properties of the model for pseudoelastie bodies followed f r o m the knowledge
of its free-energy function. Qu'ditatively f r o m here on all a r g u m e n t s are tile
s a m e in the two approaches and, therefore, we are not surprised t h a t L a n d a u
t h e o r y describes curves like those of the fig. 14 and 15, which, in pseudo-
elasticity, we saw to be consequences of free-energy curves of the shapes
of fig. 16.

(*) The notation is taken from an instructive review article by DEVONSHIRE (9).
(9) A. F. DEVO~SIIIRE: Adv. Phys., 3, 85 (1954).
316 ~. Mi~,LI,ER and K. WILMANSKI

/3) T h e d i a g r a m s o f ~ vs. E . There is a small advantage in having

a simple analytic function like (8.1) for the free energy as in L a n d n u ' s theory,
because it allows a simple representution of the pol~rizai,ion ,~s a function of E.
Indeed, in Lauda.u's theory the field E follows by differenti,%tion of (8.1) with
respect to z :

(8.2) E = X~ -t- ~::~ ~ ~:~.

These curves are draw]l in fig. 17 and it is clear thut, un(ler the @plieution of a
field, the polarization will not follow the dashed parts of the curves but rather

ff

:T" : \:
i"l : E _~2J E
i \\ . :"i ~-- K I " ~ ------

-" \i -~x 9 ~'~ :

a) c)
:Fig. 17.

the straight dotted lines. Thus the observed (a, E)-diagrams of fig. 14 appear.
I t seem~s that FALl( in 0 ~ was the first to notice that the observed
(P, D)-diag~rams of a pseudoelastic body can be summarized b y a free-energy
function of the form (8.1) with ~ replaced by D.

F o r one of the authors (K. ~YII,SrA~-SKI)this research was carried out during
his tenure as a won l I u m b o l d t research fellow in die Gesamthochschule Pader-
born nnd die Teehnische Uni~-ersit~t Berlin.

2~-P t'E N D [)2 A

The difference ~ - - / 3 .

We have
.4

~f(f~d) == NJ a~Ld 8(~,J) = (5" -- A ) J

(1o) ]?. FALK: Wie hdngt die F,reie Energie ei~ter Memory Legie,rung con der Verzerr,ung
u,ud der Temperatur ab?, ZA3IM: Sonderband on GAMM meeting 1979 Wiesbaden
(in press)9
A MODEL FOR PHASE TRANSITION IN PSEUDOELASTIC BODIES 317

and elimination of D from the two equations leads to

A

N i=1
s N - - A ~f(flJ) + ( X - - A ) J "
F o r N > > A we get
~f(fixJ) ~ ~ ( f l J )
A
since ~ A C A can at most be equal to AJ. Hence there follows t h a t fiA ~ ft.
i=1

.APPENDIX B

The size of the summands in (4.27).

W i t h (4.18) we m a y rewrite the sum (4.27) in the form

z @ . j ~ F ~ ( ~ 0 z y -~) D--C/~/~) ~i d&... d &

A ~A ) Z(.N~( )
F r o m the definition in (4.26) we conclude t h a t the Z~o~r are positive for all A.
Therefore, we have

~@..f Fl(~i)zy -~, D - - ( 1 / ~ ) E ~ i d~, . . . .

--co i~1 i~1

Zy' tD ) <

< ( m a x IF~(A)I)~ -"

(
zAf...fZ? -a) D - - ( 1 / V ~ )
i=l
Ai d~l ... d ~ A

Z~oZC'(D )
Because of the definition (4.22) of N0(A) we m a y write the n u m e r a t o r on the
right-hand side as
co

--co

Thus

~_~ ~UIF~(AOZ~A-~) D--(1/~)~fA, dA,...

i=1
< ( m a x IF,(~)l) ~.
Z~~' (D)

Since, b y (4.23), ]~(A)] < 1 holds, this inequality proves t h a t the terms in
(4.25) or (4.27) for higher values of A c o n t r i b u t e b u t little to the value of
the sum.
318 i. MULLER a n d K. WILMANSKs

9 RIASSUNTO (*)

Si p r o p o n e u n model[o t h e simul~ le p r o p r i e t ~ osserv~te dei corpi p s e u d o e l a s t i c i o l e g h e

eon m e m o r i & L a m e e e a n i e a s t a t i s t i e a del modello p e r m e t t e la deserizione di transi-
zioni d i f~se del p r i m ' o r d i n e ehe si veritieano in un,~ lega di questo tipo. Si d e s e r i v e u n a
s t r e t t a analogia f r a i l e o m p o r t a . m e n t o di un eorpo p s e u d o e l a s t i e o e di u n e o r p o
ferroelet.trieo.

(*) Traduzio?~e a cura della Redazione.

M o a e a b Aria ~ a a o n o r o n e p e x o a a n n c e n ~ o y n p y r a x Teaax.

Pe3mMe (*). - - H p e a n a r a e x c n MO;Ie~b, KoTopan BOCnpOrl3BO~nT na6n~o~aeMbIe CBO~-

cxBa n c e B ~ o y n p y r o r o Tena a n n cn~aBa, o 6 n a a a m m e r o naMnTbrO. M o d e m , , n c n o n b -
3 y m m a s CTaT~4CTI4~IecKym Mexa~nKy, n o 3 B o n n e r onnCaTb qba3oB~1e n e p e x o ~ l n e p B o r o
pojIa, rOTOpbte gMemT Mecro B Ta~OM cnnaBe. OrlHcbmaeTca a H a n o r n s M e : ~ y n o s e -
~eHHeM nceB~IOyrIpyroro x e a a H noBeAe~neM qbeppo3:ieKTpHqec~oro Tena.

(*) Ilepesec)euo pe3am/ue~t.