Binary Systems Involving the eeC atatectic"

Reaction Solid 1 Cooling Solid 2 Liquid

Heating
SIGURD WAGNER AND D. A. RIGNEY
cooling
The name " c a t a t e c t i c " is proposed for the reaction solid 1 ~
solid 2 + liquid, and a
heating
simple thermodynamic analysis is presented to aid in predicting the existence of this feature in binary phase diagrams. In addition, a survey of available phase diagrams shows
that the reaction may occur much more commonly than has been suspected.

IT

is common practice in introductory text books on

phase diagrams to examine the various types of threephase equilibria which may be evident in t e m p e r a t u r e composition phase diagrams. ~'s For binary systems
involving combinations of liquid and solid phases, 12
such three-phase features are possible, each of which
is related to a reaction of the type
cooling
phase 1 ~
phase 2 + phase 3,
heating
or
cooling
phase 1 + phase 2 .------* phase 3.
heating
Six of these are well-known reactions having generally
accepted names, such as eutecttc, peritectic, and so
forth. Of the remaining six, some have no recorded
cases in metal systems, and some may not occur at
all. One type, however, may deserve more attention
than it has received. It is the main subject of this
paper.

NOMENCLATURE
At first sight, the reaction
cooling

solid 1 ,

heating

solid 2 + liquid

may appear rather peculiar, because it indicates that a

solid phase decomposes upon cooling into a liquid and
a second solid phase. In effect, the solid can partly
" m e l t " when the temperature is lowered, and it can
solidify again when the temperature is raised. This
kind of topsy-turvy behavior is allowed thermodynamically, and indeed, examples of this reaction do exist
in metallic systems. 4"e
Gordon states that " T h i s invarlant reaction has as
yet no generally accepted name but the designation
' m e t a t e c t i c ' is sometimes used. ''2 Rhines provides
no name for the reaction, but he points out that the
SIGURDWAGNERis Member of Technical Staff, Bell Telephone
Laboratories, Holmdel, N.J. 07733. D. A. RIGNEYis Associate
Professor, Department of Metallurgical Engineering, The Ohio State
University, Columbus, Ohio 43210.
Manuscript submitted November 12, 1973.
METALLURGICALTRANSACTIONS

term " m e t a t e c t i c " has been used to describe the p e r i tectoid. 1 Prince uses the term " m e t a t e c t i c , " and he
also notes that " P e r i t e c t o i d reactions are occasionally
r e f e r r e d to as metatectic reactions. "s He also points
out that the word segment " - t e c t i c " is unsuitable for
use with a reaction involving only solid phases, since
it has to do with melting.
Since " m e t e - " means '%etween," "with," " a f t e r , "
or " l a t e r , " the t e r m metatectic might be a sensible
choice for the reaction under discussion, since " a f t e r "
initial freezing a material can partly remelt " l a t e r . "
However, since the term metatectic has been used,
perhaps unwisely, for another type of reaction, it might
be better to abandon it altogether and use a new t e r m
to minimize confusion.
A suggested new t e r m is " c a t a t e c t i c . " This is based
on the Greek word " k a t e , " which means "down." The
term would then literally translate as "down m e l t " or
"down melting," which would be reasonably descriptive, and the word would continue the tradition of using
Greek roots for phase diagram features. The term
" c a t a t e c t i c " will be used for the remainder of this
paper.
The solid phase coexisting with the liquid at lower
temperatures generally has a relatively close-packed
structure, frequently fcc or hcp. It will be called the
3/phase. The single solid phase which exists at equilibrium above the catatecttc temperature is frequently
bcc, or some other structure which is not as closely
packed as 3/. It will be called the 5 phase.
In binary systems, three kinds of catatectics can
exist. If both solids 3/and 5 are solid solutions based
on allotroplc modifications of the solvent, a terminal
catatectic exists. This is the type most frequently encountered; it is shown in Fig. l(a). The corresponding
free energy v e r s u s composition diagram at the catatectic temperature is shown in Fig. l(b). An example
is the F e - Z r system. When the 3/and 5 phases are both
compounds or intermediate phases, the system will be
labelled a compound catatectic (Figs. 2(a) and 2(b)).
An example is the Cu-Sn system. The third type would
involve a terminal solid solution 5 and an intermediate
phase 7, as shown in Figs. 3(a) and 3(b). The only
known example of such a mixed catatectic system is
Ag-Li, in which the a and ~ solid phases are involved.
For all three types of catatectic systems, the single
temperature at which the phase Y t r a n s f o r m s directly
to the phase 5 shall be labelled T tl.
VOLUME 5. OCTOBER 1974-2155

Tml
I---

Tr
I-!

xS

xc

xL

(a)

COMPOSITION x
(a)

G,Io(L)
T=T c
G~o(B )

T :T c
Gto()')

>r
n~
t~
Z
W

W
W
b~
!
!

xs

xC

nn
nn

xL

(b)
Fig. 1--(a) P a r t i a l b i n a r y T - x d i a g r a m showing a t e r m i n a l

catatectic. (b) Free energy diagram for the three phases in

equilibrium at Tc.

CONDITIONS FOR THE EXISTENCE

OF CATATECTICS
The m o s t c o m p l e t e d i s c u s s i o n of e a t a t e e t i c ( m e t a teetic) s y s t e m s ts in the book by P r i n c e . 3 He p r e s e n t s
a s e r i e s of f r e e e n e r g y d i a g r a m s of the type given in
Fig. l(b) and he d e s c r i b e s the s e q u e n c e of events which
o c c u r s d u r i n g s o l i d i f i c a t i o n for alloys involving the
e a t a t e e t i e r e a c t i o n . However, f u r t h e r a n a l y s i s does
not a p p e a r to e x i s t tn the l i t e r a t u r e .
In this section, s o m e s i m p l e t h e r m o d y n a m i c r e l a t i o n s h i p s will be d i s c u s s e d and applied to t e r m i n a l
e a t a t e e t i e s y s t e m s , and s i m p l e g u i d e l i n e s will e m e r g e
which can be used to p r e d i c t the p r e s e n c e of a t e r m i n a l
e a t a t e c t i e r e a c t i o n in a given b i n a r y a l l o y s y s t e m .
At the e a t a t e e t t c t e m p e r a t u r e T c < T t ~, liquid L and
s o l i d s y and 5 a r e tn e q u i l i b r i u m , as shown in Figs. 1,
2, and 3. Even with a c u r s o r y e x a m i n a t i o n of a phase
d i a g r a m , one t a n see if the liquid is s t a b l e below Ttx.
It will not be s t a b l e at T < Tt i if
a) The 5 solid solution is m o r e stable than the liquid
L at T < Tt~ at all c o m p o s i t i o n s w h e r e 6 and L coexist,
o r , the m e l t i n g point of 8 is not s u f f i c i e n t l y l o w e r e d by
the addition of solute. This ease of high s t a b i l i t y of the
8 - s o l u t i o n with r e s p e c t to the liquid often o c c u r s when
the 6 m o d i f i c a t i o n s of s o l v e n t and solute f o r m a c o n t i n uous s e r i e s of solid s o l u t i o n s , as in the B a - C a , C e - L a ,
F e - C r , F e - C o , and G d - L a s y s t e m s ;
2156-VOLUME 5, OCTOBER 1974

COMPOSITION

(b)
Fig. 2--(a) Partial binary T - x diagram showing a compound
catatectic. (b) F r e e energy d i a g r a m for the t h r e e p h a s e s in
equilibrium at Tc.

b) An i n t e r m e d i a t e phase in e q u i l i b r i u m with the 8

solid solution is m o r e stable than the liquid phase L
at T < T t~. E x a m p l e s a r e F e - N b and Fe-Hf.
Once a liquid phase L has b e e n found to e x i s t in e q u i l i b r i u m with a t e r m i n a l solid solution at T < Tt,, then
the p r i n c i p a l r e q u i r e m e n t for a c a t a t e c t i c to exist is a
l o w e r i n g of Ttl upon addition of solute. The y phase
can then be In e q u i l i b r i u m with the liquid phase except
for the s p e c i a l ease of y - l o o p f o r m a t i o n , i . e . , when a
low t e m p e r a t u r e phase exhibits a s t r u c t u r e i d e n t i c a l
to that of 6. This o c c u r s for s e v e r a l s o l u t e s in Fe,
e . g . , Fe-A1, F e - B e , F e - C r , Fe-Si, and so on. For s y s t e m s not f o r m i n g y - l o o p s , the r e q u i r e d l o w e r i n g of T t x
will o c c u r if, at T = Tt, and n e a r x = 0, the Gibbs f r e e
e n e r g y for the 8 phase, C 6, is m o r e negative than that
for the y phase, G~/, as shown in Fig. 4(a).
T h e r e is some advantage to plotting the function G
+ TS id (Fig. 4(b)) r a t h e r than the free e n e r g y G itself,
s i n c e the r e v i s e d function has a finite slope at x = 0.
The t e r m T S id is the magnitude of the e n t r o p y c o n t r i bution to the f r e e e n e r g y for an ideal solution. It is
then p o s s i b l e to c o m p a r e the slopes of (G + T s i d ) 6 and
(G + T s i d ) 7 to see which is s m a l l e r (less positive or
m o r e negative).
METALLURGICAL TRANSACTIONS

T = Ttt

G20 (),')

I-

G2o (B)
B

G.IO ()")
GtO (8)

I-

G(8)
COMPOSITION x
(a)

0
X
(a)

o
>-

(.9

T=T c

n~
hi
Z
IJJ

G20 (~')
G20 (8)

GtO (7")

LU

G40 (8)
(G .f- Tsid) y

I=.
(/)
m
m

(G -+'TS id)8

COMPOSITION x
(b)

Fig. 3 - - ( a ) P a r t i a l binary T - x d i a g r a m showing a mixed c a t a tectic. (b) F r e e energy d i a g r a m for the t h r e e p h a s e s in equilibrium at T c .

If one u s e s the m o s t s i m p l e model for n o n i d e a l s o l u t i o n s a s s u m i n g r e g u l a r solid s o l u t i o n s , then the c o n d i tion for c a t a t e c t l c s is

G5 - Cy = (1 - x)[G,o(5) - G,o(),)] + x [G2o(6) - C2o('Y)]

+x(1-x)[Bs-By]
<0 a t T = Tt,,
[1]
where x ts the a t o m i c f r a c t i o n of c o m p o n e n t 2 (the s o l ute), Glo and G2o a r e the Gibbs f r e e e n e r g i e s of the pure
c o m p o n e n t s , and B 5 and B~, a r e the r e g u l a r solution p a r a m e t e r s for the 8 and the ), solid solution, r e s p e c t i v e l y .
The condition
Gs-Gy<O
at T= Ttl
can be s i m p l i f i e d to the r e q u i r e m e n t that

~/ax(G 6 - G y )

< 0 at T = Tt, and x = 0.

[2]

By u s i n g this quantity one e l i m i n a t e s the c o n c e n t r a tion dependent t e r m s . Since G~o(6) = G~o(V) at Tt~, the
c r i t e r i o n for a l o w e r i n g of the t r a n s f o r m a t i o n t e m p e r a t u r e Tt ~ b y the addition of solute is

a/ax(G 5 - Gy) = [G=o(6) - G2o(.y)] + [B 5 - By] < 0

a t x = 0.

METALLURGICAL TRANSACTIONS

[3]

X
(b)

Fig. 4--(a) F r e e energy diagram for the y and 5 p h a s e s at the

allotropic t r a n s f o r m a t i o n t e m p e r a t u r e T t i . (b) T h e function
(G + T S i d ) for the 3' and 5 p h a s e s at T = T t l .

The t e r m [B 5 - By] c o n t a i n s the effects of d e v i a t i o n s

f r o m ideal s o l u t i o n b e h a v i o r for the 5 and ), solid s o l u t i o n s . N u m e r o u s p h e n o m e n a can lead to nonideal s o l u t i o n s and to d i f f e r e n c e s b e t w e e n B 5 and B1,. Some of
t h e s e a r e difficult to evaluate, e s p e c i a l l y without d e t a i l e d knowledge of the phase d i a g r a m . E x a m p l e s a r e
the f o r m a t i o n of i n t e r s t i t i a l solutions and c h a n g e s in
the f r e e e l e c t r o n c o n c e n t r a t i o n . On the o t h e r hand, a s
d i s c u s s e d in the Appendix, one can r o u g h l y e s t i m a t e
the effect on [B 5 - By] of two c o n t r i b u t i o n s to n o n i d e a l
b e h a v i o r . The l a t t i c e s t r a i n r e s u l t i n g f r o m d i f f e r e n t
s i z e s of s o l v e n t and solute a t o m s tends to s t a b i l i z e the
5 phase with r e s p e c t to ),, i.e., [B 5 - B T ] s t r a i n < 0. The
d i f f e r e n c e in the e l e c t r o n e g a t i v i t y of s o l v e n t and solute
p r o b a b l y s t a b i l i z e s y with r e s p e c t to 5, i.e.,
[B 5 - B y]electronegativity > 0.
Though IB 5 - By1 could be c o m p a r a b l e with lG2o(5)
- G~o()')I, for m a n y alloys it m a y be c o n s i d e r a b l y
s m a l l e r . F o r such c a s e s , it is i n t e r e s t i n g to e x a m i n e
the p a r t i a l condition

[G,o(~ ) - C,o(y)] < 0.

[4]
VOLUME 5,OCTOBER 1974-2157

If T t i i s t h e t e m p e r a t u r e f o r t h e ~ - - 6 t r a n s f o r m a t i o n
f o r p u r e c o m p o n e n t i, a n d if h H t i i s t h e e n t h a l p y c h a n g e
for this transformation, then it can be shown simply
that
G 2 o ( 5 ) - G2o(Y) ~ A H t 2 ( 1 -

Tt,/Tt2).

[5]

T h u s , if Tt2 i s l e s s t h a n Tt~ , a c a t a t e c t i c m i g h t b e e x pected. This simple condition should be useful for pred i c t i n g c a t a t e c t i c r e a c t i o n s , e s p e c i a l l y if AHt2 ( 1 - T t ~ /
Tt~) i s s t r o n g l y n e g a t i v e , s i n c e i t w o u l d t h e n b e m o r e
l i k e l y t h a t [B 6 - B~,] c o u l d b e s a f e l y n e g l e c t e d .

RESULTS AND DISCUSSION

Table I is presented as a test of Eq. [5]. It lists the
known binary terminal catatectic systems for which
enthalpy data are also available. Onlythe prototype
transformation 6(bcc) --- y(fcc) is considered. The
temperature and enthalpy of transformation for stable
modifications, includingall solvents and several solutes, were taken from the reference work by Hultgren
and coworkers, 7 or from the book by Kubaschewskl et
al. s For transformations involvingmetastable solutes,
Tt~ and AH~2are the values calculated by Kaufmanand
Bernstein. Withthe exception of Mn-Cu, the values
for AHt2(I - Tt,/Ttz ) show an acceptable spread.
Though the C e - M n value has the wrong sign, it is
small, and one might still predict a catatectlc if, for
i n s t a n c e , AHt2 ( 1 - T t z / T t 2 ) <_ + 1 0 0 0 J / m o l e ( + 2 3 9
cal/mole). This would allow for some influence from
t h e [B5 - B~,] t e r m , w h i l e r e t a i n i n g t h e s i m p l i f i e d
g u i d e l i n e of E q . [5].
However, the Mn-Cu result is large and positive, and
t h i s l e a v e s t h e p i c t u r e s o m e w h a t c o n f u s e d . It s h o u l d
b e p o i n t e d o u t t h a t v a l u e s f o r both A H t z a n d Tt2 w e r e
obtained by calculation ~ rather than by experiments
f o r t h i s s y s t e m . I m p r o v e d a g r e e m e n t w o u l d of c o u r s e
r e s u l t if t h e a c t u a l v a l u e of Tt2 f o r M n - C u w e r e c l o s e r
t o t h e m e l t i n g p o i n t of c o p p e r . In f a c t , if Tt2 ~- Trap2,
t h e n a s m a l l n e g a t i v e v a l u e w o u l d a p p e a r in T a b l e I
for this system.
R a t h e r t h a n d e v o t e t o o m u c h e f f o r t to " e x p l a i n i n g "
the uneven agreement between predictions based on
E q . [5] a n d t h e a p p r o x i m a t e n u m b e r s in T a b l e I, p e r h a p s
it would be more sensible to withhold judgement until

more data are available. The sample in Table I is, after

all, very small.
A survey of phase diagrams in Refs. 4 to 6 will lead
to the conclusion that a surprisingly large number of
binary systems may include a terminal catatectic. Some
may even include more than one. An example Is Ce-Mn,
which was included in Table I because it has a catatectic at the Ce side of the phase diagram, s At the Mn side
of the same diagram, the value of AHt2(I - Tt,/Ttz)
would be - 1200 J/mole (- 287 cal/mole). This would
indicate a catatectlc involvingthe y and 6 phases of Mn,
and this would be consistent with the limited data shown
for Ce-Mn in Ref. 4. The case of Ce-Mn also shows
clearly that a prediction based on relative values of
Tt, and Tt2 Is inadequateby itself, since the term
(i - Tt~/Tt2) will have different signs for the two sides
of the phase diagram.
Many other incomplete or incorrect phase diagrams
published In Refs. 4 to 6 could be improved by inclusion
of one or more catatectic reactions. Systems involving
Ca, Fe, Am, and Th Cocc ~ fcc) and many of the rare
earths (bcc ~ hcp) Include the necessary 5 ~ ~ transformation, and in many cases a catatectic is indicated
by either the presence of a suitable invariant temperature line or by the ease with which a thermodynamically
feasible phase diagram can be completed, taking account
of all allotroplc transformations of the components. For
some of these systems there may have been some reluctance on the part of the investigators to include the
catatectlc, since this is a relatively unfamiliar feature
and one which implies unusualresponses to temperature changes. Also many catatectlcs will be difficult
to detect by thermal analysis because of the small
amount of heat involved in the reaction. This might
explain why so few catatectics have been included in
published phase diagrams, and why so little discussion
is included in Refs. 4 to 6 as to the possibility or likelihood of completing a given phase diagram wlth the
boundary lines appropriate to a catateetic.
The binary systems presented in Table H are those
which either have a knownterminal catatectic or in
which a catatectic Is a reasonable possibility. In addition, catatectlcs Involvingthe bcc ~ hop transformation can be expected to occur in rare earth element
solvents. The value of ~d'/ta( I - Tt,/Tt2) is given

Table I. Known Terminal C4tatectir~ 4"6

Component l
(SoZvent)

Component 2
(Solute)

T(K) _ _

Imp t

Trnp 2

Tt ,

Tt2

A Ht2
(J/mole)

AHt2 ( 1-Trl /Tt2 )

(J/mole)

1407
724a
749b
1250c
255c
1875c
1003
940c

1880d
84a, e
1840b,e
1050c
960c
6300c
3000~
2990c

+540
_ 650f

Ce
Ce

Mn
Pu

1068
1068

1518
913

1003
1003

Fe
Fe
Mn
Th
Th

Zn
Zr
Cu
Ce
U

1810
1810
1518
2023
2023

693
2130
1356
1068
1403

1665
1665
1407
1673
1673

-350
-5300
"1580
-2000
-2300

aFCC -* Body-centered tetragonal (Ref. 5).

bBody.centered tetragonal ~ BCC (Ref. 5).
CRef. 9.
dRef. 7.
eRef. 8.
fCalculated using Tm = 749 K and AHta = 1924 J/mole.

2158-VOLUME 5, OCTOBER 1974

METALLURGICAL TRANSACTIONS

Table II. Terminal Catatectics, Known and Possible4"6

Ca-Cd
Ca-Li
Ca-Na
Ca-Zn
Ce-Ag
Ce-AI
Ce-Au
Ce-Fe*
Ce.Mn*
Ce-Ni
Ce.Pu
Ce-T1
Fe-Gd
Fe-La*
Fe-Pb
Fe-Pu*
Fe-S
Fe-Zn
Fe-Zr

+420
+1900
+5200
-2000
+540
-650
-860
-1450
-2300
-350
-5300

La-Ag
La-AI
La-Au
La-Cu
La-Ni
La-Pb
La-Pu
La-Sb
La-Sn
La-TI
La-Zn
Mn-Ag*
Mn-As
Mn-Bi
Mn-Ca
Mn-Cu
Mn-Gd*
Mn-ln
Mn.La*
Mn-Li*

+1600
+4500
+2500
-1000
- 1000
+90
+1050
-350
-850
+1580

Table III. Catatectic Systems Involving a ~ompound 4"6

Ag-Ga
Ag-ln
Ag-Li

Mn-P
Mn-Y*
Mn-Si
Mn-Pu
Mn-U*
Sr-Li
ThAI
Th-Be
Th-Bi
Th-Ce
Th-Cu
Th-Hf
Th-In
Th.Pd
Th-Pt
Th-Rh
Th-Ru
Th-Ti
Th-U
TI-As

Bi-Mg

- 1700
- 1500
+1700
-5400
-125
-2000
+650
-2000

to G , V , . K a u f m a n and B e r n s t e i n ~ u s e t h e p r o p o r t i o n a l ity

G1 cc HI,s/V1
to e l i m i n a t e V, ( ~ - / , , s is the h e a t of s u b l i m a t i o n of t h e
solvent):

W c c ~2 H l , s ( V z / V l _ l ) Z
-5300
-2300

T h e m a g n i t u d e of H~,s i s i n d e e d of the o r d e r of t h a t
of G , V , . T h i s l e a d s to a u s e f u l a p p r o x i m a t i o n f o r W,

W ~- ~ H,,s(V2VI-1) 2

*More than one catatectic possible.

The value for AHr2(1-Ttl/Tt2)inJ/mole is givenwhere sufficient data are
available.

where the required data are available. Most data were

t a k e n f r o m R e f . 9. It is i n t e r e s t i n g to n o t e that, u s i n g
R e f . 9, t h e e l e m e n t s Cu, Ag, and A1 a l l l e a d to r e l a t i v e l y l a r g e p o s i t i v e v a l u e s . It s h o u l d b e a p p a r e n t t h a t
e v e n if s o m e of the s y s t e m s l i s t e d in T a b l e II p r o v e to
h a v e no c a t a t e c t i c , t h i s t y p e of r e a c t i o n m a y b e m u c h
more common than has been assumed previously.
T a b l e III i n c l u d e s t h e s m a l l e r n u m b e r of b i n a r y s y s t e m s in w h i c h a c a t a t e c t i e i n v o l v i n g a c o m p o u n d a p p e a r s to e x i s t .
APPENDIX

- L

)']

[A4]

[ ~ G zV~ (Y z

Iv,

-~ - ~

- 1

)' 7 o r

6at T1

This result suggests that the strain energy contribution

to n o n i d e a l s o l u t i o n b e h a v i o r t e n d s to s t a b i l i z e t h e 5
with r e s p e c t to t h e 7 p h a s e , and t h e r e f o r e f a v o r s t h e
o c c u r r e n c e of c a t a t e c t i c s .

[All

1)a] 6 -

[A5]

p e r m o l e of s o l u t e at i n f i n i t e d i l u t i o n , z~ G, is t h e s h e a r
m o d u l u s of t h e h o s t c r y s t a l and V,, r , and V2, r 2 a r e t h e
m o l a r v o l u m e s and t h e a t o m i c r a d i i of t h e s o l v e n t and
of t h e s o l u t e r e s p e c t i v e l y .
In o r d e r to d e t e r m i n e w h e t h e r t h e s t r a i n e n e r g y t e r m
favors the close-packed phase 7 or the less closep a c k e d p h a s e 6, W 7 and W 5 s h o u l d b e c o m p a r e d . If
W 6 - Wy < 0, t h e s i z e e f f e c t t e n d s to s t a b i l i z e 6 with
r e s p e c t to 7. T h e e x p r e s s i o n to e x a m i n e is t h e r e f o r e
-

,skv

Vz

[B 5 - B T ] s t r a i n

W= ~ G 1 V , ( V a / v , - 1) 2 = ~ C l V ~((r~/rz) s - 1) 3

IVz (V 2 / V z

WT-~[~H,,s(~-~21 - 1 ) ' ] 6

L i t t l e i n f o r m a t i o n is a v a i l a b l e a b o u t t h e m o l a r v o l u m e s
of h i g h t e m p e r a t u r e m o d i f i c a t i o n s , in p a r t i c u l a r of the
m e t a s t a b l e p h a s e s . T h e r e f o r e it is m o s t e x p e d i e n t to
a s s u m e t h a t t h e r a t i o of t h e m o l a r v o l u m e s r e m a i n s
c o n s t a n t d u r i n g t h e 6-7 t r a n s f o r m a t i o n , i.e.,

Since a solute atom will generally have a different

s i z e f r o m s o l v e n t a t o m s in a s o l i d s o l u t i o n , an e l a s t i c
s t r a i n e n e r g y c o n t r i b u t i o n s h o u l d b e i n c l u d e d in e x p r e s s i o n s f o r t h e f r e e e n e r g y of s o l i d p h a s e s . F o r a
m o l e of h o s t c r y s t a l , t h i s e l a s t i c e n e r g y i s g i v e n b y

W 7 = [~ G

W6 -

With H z,s (6) - H,, s (7) = - A H t l we o b t a i n

1. S t r a i n E n e r g y and t h e 5 ~
Transformation

[A3]

T h e s t r a i n e n e r g y c o n t r i b u t i o n to t h e r e g u l a r s o l u t i o n
t e r m in Eq. [5] is t h e n

[B6-BT]strain:

W5

Cu-Sn
Fe-Zn
Li-Sr

z)~]~

2. E l e c t r o n e g a t i v i t y
D i f f e r e n c e s in t h e e l e c t r o n e g a t i v i t y b e h a v i o r of s o l v e n t and s o l u t e , - c o n t r i b u t e to a n e g a t i v e d e v i a t i o n f r o m i d e a l i t y . T h e r e s u l t i n g p o r t i o n of t h e r e g u l a r
s o l u t i o n p a r a m e t e r is z*

B e = - 96,500 n ( - 2 J / m o l e .

[A6]

n is t h e n u m b e r of b o n d s p e r a t o m f o r m e d b e t w e e n 1
and 2. T h e e l e c t r o n e g a t i v i t y c o n t r i b u t i o n to the r e g u l a r s o l u t i o n t e r m in Eq. [5] is
[B 5 - By] e = - 96,500 (

2 (n 5 - n 7)

[A7]

[A2]
D a r k e n and G u r r y *~ m e n t i o n t h a t G,V, d o e s not v a r y
m u c h f r o m m e t a l to m e t a l o r w i t h t e m p e r a t u r e . T h e y
a s s i g n a n a v e r a g e v a l u e of 250 k J / m o l e (60 k c a l / m o l e )
METALLURGICAL TRANSACTIONS

There
is set
which
other

a r e two a p p r o a c h e s to e s t i m a t i n g n. 11 In o n e , n
e q u a l to t h e m a x i m u m v a l e n c y of t h e c o n s t i t u e n t s ,
m a k e s it i n d e p e n d e n t of c r y s t a l s t r u c t u r e . In t h e
a p p r o a c h , t h e n u m b e r of b o n d s p e r a t o m is not
VOLUME 5, OCTOBER 1974-2159

only determined by the valency, but also by the coordination number which is higher for denser packing. Since
an atom in 5 has a lower number of nearest neighbors
t h a n a n a t o m i n 7, n 6 - n~, < 0, a n d [B 6 - B3,]e > O.
Thus the electronegativity
contribution may stabilize
w i t h r e s p e c t t o 5, a n d t h e r e f o r e d i s f a v o r s c a t a t e c t i c s .

RE FERENCES
l. F. N. R/fines: Phase Diagrams in Metallurgy, McGraw-Hill, New York, 1956.
2. P. Gordon: Principles of Phase Diagrams in Materials Systems, McGraw-HiU,
New York, 1968.
3. A. Prince: Alloy Phase Equilibria, Elsevier Publishing Co., AmsterdamLondon-New York, 1966.

2 1 6 0 - V O L U M E 5, OCTOBER 1974

4. M. Hansen and K. Anderko: The Constitution of Binary Alloys, McGraw-Hill,

New York, 1958.
5. R. P. Elliott: Constitution oflh'nary Alloys, First Supplement, McGraw-Hill,
New York, 1965.
6. F. A. Shunk: Constitution of Binary Alloys, Second Supplement, McGrawHill, New York, 1969.
7. R. Hultgren, R. L. Orr, P. D. Anderson, and K. K. Kelley: Selected Values of
Thermodynamic Properties o.f Metals and Alloys, Wiley, New York, 1963, and
Supplements.
8. O. Kubaschewski, E. LI. Evans, and C. B. Alcock: Metallurgical Thermochemistry, 4th ed., Pergamon Press, London, 1967.
9. L. Kaufman and H. Bemstein: Computer Calculation of Phase Diagrams,
Academic P~ess,New York, 1970.
10. L. S. Darken and R. W Gurry: Physical Chemistry of Metals, McGraw-Hill,
New York, 1953.
11. B. W. Mott: Phil. Mag., 1957, vol. 2, pp. 259-83.

METALLURGICAL TRANSACTIONS