Thermodynamics and Phase Diagram

of the Fe-C System

JOHN CHIPMAN

A c r i t i c a l r e v i e w of published data p r o v i d e s a f a i r l y a c c u r a t e knowledge of the t h e r m o d y n a m i c

p r o p e r t i e s of a l l of the p h a s e s of the s y s t e m F e - C that a r e stable o r m e t a s t a b l e at a t m o s p h e r i c
p r e s s u r e . S e l e c t e d data a r e shown a s t a b l e s and e q u a t i o n s . A p r o p o s e d phase d i a g r a m differs
only slightly f r o m o t h e r s r e c e n t l y p u b l i s h e d but has the following f e a t u r e s . P e r i t e c t i c c o m p o s i t i o n s and the c~-~ e q u i l i b r i u m a r e shown to a g r e e with m e a s u r e d values of the a c t i v i t y of i r o n
in the solid and liquid solutions and the t h e r m o d y n a m i c p r o p e r t i e s of pure i r o n . Of a l l the r e ported c a r b i d e s of i r o n only two m a y be studied u n d e r e q u i l i b r i u m c o n d i t i o n s . The s o l u b i l i t i e s
of c e m e n t i t e and of x - c a r b i d e in c~-Fe a r e deduced from m e a s u r e d e q u i l i b r i a . Both a r e m e t a s t a b l e at a l l t e m p e r a t u r e s with r e s p e c t to g r a p h i t e and its s a t u r a t e d solution in i r o n . The Xcarbide becomes more stable than cementite below about 230~ Certain published data on ~carbide permit an estimate of its free energy as a precipitate during the aging process.

P R O B A B L Y e v e r y o n e who a t t e m p t s to do p r e c i s e
e x p e r i m e n t a l m e a s u r e m e n t s on b i n a r y a l l o y s of i r o n
and c a r b o n feels t e m p t e d to t r y his hand at r e v i s i n g
the F e - C d i a g r a m . Now that I have been a s k e d to p r e p a r e a d i a g r a m for the Metals Handbook of the A m e r ican Society for M e t a l s , I a m no longer able to r e s i s t
this t e m p t a t i o n . A c t u a l l y the d i a g r a m of H a n s e n a n d
A n d e r k o I is v e r y good and the a m o u n t of r e v i s i o n r e q u i r e d is quite m i n i m a l . The s a m e can be said of the
m o r e r e c e n t d i a g r a m of E l l i o t t , G l e i s e r , and R a m a k r i s h n a . 2 The l a t t e r had the advantage of the v e r y a c c u r a t e d e t e r m i n a t i o n of the ~ - s o l i d u s by Benz and
E l l i o t t 3 but o m i t t e d th~ n e a r l y s i m u l t a n e o u s p u b l i c a tion of data on the liquidus by Buckley and H u m e R o t h e r y . 4 "In t h e i r s o m e w h a t o l d e r d i a g r a m D a r k e n
and G u r r y ~ saw to it that the b o u n d a r y lines w e r e cons i s t e n t with m e a s u r e d p r o p e r t i e s of the p h a s e s i n volved and with the laws of t h e r m o d y n a m i c s . This
p r o c e d u r e can be r e c o m m e n d e d to anyone who s e t s
out to c o n s t r u c t a phase d i a g r a m . The t h e r m o d y n a m i c
p r o p e r t i e s of the i n d i v i d u a l c o m p o n e n t s and in p a r t i c u l a r t h e i r p a r t i a l m o l a r p r o p e r t i e s within the h o m o g e n e o u s phases provide a m o r e complete p i c t u r e of
the s y s t e m than does the p h a s e d i a g r a m a l o n e . It is
i n t e n d e d that this p a p e r s e r v e a s a review and e v a l u a tion of this kind of data with a view to r e v i s i o n of the
c o m p i l a t i o n of H u l t g r e n , O r r , A n d e r s o n , and K e l l e y . 6
The p o s s i b i l i t i e s for m e a n i n g f u l r e v i s i o n r e s t on
s e v e r a l m o r e r e c e n t p u b l i c a t i o n s . Scheil, S c h m i d t ,
and Wt]nning7 d e t e r m i n e d the t h e r m o d y n a m i c p r o p e r t i e s of F e - C a u s t e n i t e s and c e m e n t i t e u s i n g the COCOz e q u i l i b r i u m . A s i m i l a r study of a u s t e n i t e by
B a n - ya, E lliott, and C h i p m a n 6 extended the t e m p e r a t u r e r a n g e and d e r i v e d s i m p l e m a t h e m a t i c a l s t a t e m e n t s for the t h e r m o d y n a m i c p r o p e r t i e s of the c o m ponents. F o r m e r discrepancies regarding solubilities
of g r a p h i t e and c e m e n t i t e in the c~-phase have a p p a r JOHN CH1PMAN, a Fellow of T.M.S. and A.S.M., is Professor
Emeritus, Department of Metallurgy and Materials Science, Massachusetts Institute of Technology, Cambridge, Mass., and Consultant, Inorganic Materials Research Division, Lawrence Radiation Laboratory,
University of California, Berkeley, Calif.
Manuscript submitted March 22, 1971.
METALLURGICALTRANSACTIONS

ently b e e n g r e a t l y r e d u c e d by the r e c e n t work of

Swartz .9
Of e q u a l i m p o r t a n c e has b e e n the r e c e n t m a r k e d
i m p r o v e m e n t in the data on the p r o p e r t i e s of pure
i r o n . The heat of fusion of i r o n has been lowered
s o m e 10 pct by r e c e n t s t u d i e s of F e r r i e r and Olette 1~
and of M o r r i s , F o e r s t e r , Schultz, and Z e l l a r s . '~ The
heat c a p a c i t y of the solid, p a r t i c u l a r l y in the y - r a n g e
has been r e v i s e d by the work of Olette and F e r r i e r , ~2
A n d e r s o n and H u l t g r e n , ~3 D e n c h and K u b a s c h e w s k i , ~4
B r a u n , is and of W a l l a c e , S i d l e s , and D a n i e l s o n . 16 All
of these s t u d i e s of the t h e r m a l p r o p e r t i e s of i r o n have
been r e v i e w e d by O r r and C h i p m a n 17 who d e r i v e d p r e cise values for the d i f f e r e n c e s in Gibbs free e n e r g y
b e t w e e n the s e v e r a l stable o r m e t a s t a b l e p h a s e s .
In addition it m u s t be pointed out that r e v i s i o n is
r e q u i r e d by the adoption of the new I n t e r n a t i o n a l P r a c t i c a l T e m p e r a t u r e Scale of 1968 '8 a c c o r d i n g to which
a s e c o n d a r y r e f e r e n c e , the m e l t i n g point of p a l l a d i u m
has been r a i s e d f r o m 1552 ~ to 1554~
On this scale
the m e l t i n g point of i r o n b e c o m e s 1538~ while lower
fixed points r e q u i r e s m a l l e r o r n e g l i g i b l e a d j u s t m e n t .
Since p r a c t i c a l l y a l l useful data a r e given on the 1948
s c a l e , this s c a l e will be used in s o m e c a l c u l a t i o n s and
a d j u s t m e n t s will then be applied to c o n f o r m to the new
s c a l e . To avoid a m b i g u i t y , t e m p e r a t u r e s will be d e s ignated (48) o r (68). F o r m a n y p u r p o s e s the d i f f e r e n c e
is t r i v i a l .

I) THE AUSTENITE F I E L D
The fcc solid solution is the h e a r t of the b i n a r y s y s tem and its p r o p e r t i e s and b o u n d a r y l i n e s a r e r a t h e r
w e l l - k n o w n . The a c t i v i t y of c a r b o n a s a function of
t e m p e r a t u r e and c o m p o s i t i o n has b e e n d e t e r m i n e d by
m a n y o b s e r v e r s , chiefly through s t u d i e s of the equilibria
C + 2H2= CH4

[1]

C + COz = 2CO

[2]

Among the older investigations of reaction [2] those

of D~nwald and Wagner19and of Smith2~are in agreement with the more recent work of Scheil7 e t a l . (ex-

VOLUME 3, JANUARY 1972-55

c e p t a t t h e h i g h e s t c a r b o n c o n c e n t r a t i o n s ) a n d of B a n y a 8 e t a l . S t u d i e s of r e a c t i o n [1] h a v e b e e n s u b j e c t to
e r r o r s e s p e c i a l l y a t low c a r b o n l e v e l s , d u e to r e a c t i o n of m e t h a n e w i t h r e s i d u a l g a s i m p u r i t i e s . T h i s i s
t h o u g h t to h a v e b e e n r e s p o n s i b l e f o r t h e d i f f e r e n c e s
o b s e r v e d b y S m i t h 2~ b e t w e e n a c t i v i t y c o e f f i c i e n t s d e t e r m i n e d b y t h e two e q u i l i b r i a . It m a y h a v e a c c o u n t e d
also for the disagreement between the values accepted
h e r e a n d t h o s e of S c h e n c k a n d K a i s e r 2~ a n d of S c h t ] r m a n n , S c h m i d t , a n d W e g e n e r . 22 S t u d i e s b a s e d o n r e a c t i o n [2] h a v e not b e e n i m m u n e to s i m i l a r b u t g e n e r a l l y
s m a l l e r e r r o r s w h i c h t e n d to b e c o m e g r e a t e r w i t h
increasing temperature and carbon content.
Ban-ya, E lliott, and Chipman 8 covered a wide range
of c o m p o s i t i o n a n d t e m p e r a t u r e a n d in t h e i r a n a l y s i s
of t h e d a t a i n c l u d e d c o n s i d e r a t i o n of t h e e a r l i e r w o r k .
T h e y e x p r e s s e d t h e i r r e s u l t s i n t e r m s of a v e r y s i m p l e m o d e l i n w h m h t h e a c t i v i t y of a n i d e a l i n t e r s t i t i a l
s o l u t e is p r o p o r t i o n a l to t h e r a t i o of f i l l e d to u n f i l l e d
interstitial sites. Since there is one interstitial site
per lattice atom, the ideal activity at great dilution is

ac ~ nc/(riFe -- nC ) = Y C / ( 1 -- YC ) = ZC

[3]

w h e r e YC i s t h e a t o m r a t i o n O / r i F e a n d t h e t e r m
Y C / ( 1 - YC) m a y b e a b b r e v i a t e d a s z C . D e v i a t i o n s
from the ideal at finite concentrations were repres e n t e d by a n a c t i v i t y c o e f f i c i e n t V#c = a c / z c w h i c h
w a s f o u n d to b e r e l a t e d to t h e c o n c e n t r a t i o n , YC b y
the simple equation

tn V#c : tn ff(~ + OcY C

[4]

where ~
i s i t s v a l u e a t i n f i n i t e d i l u t i o n a n d 0C i s a n
i n t e r a c t i o n c o e f f i c i e n t , b o t h b e i n g f u n c t i o n s of t e m perature.
In t h e i r plot of log K v s 1/T t h e y f o u n d t h a t a
s t r a i g h t l i n e b a s e d o n d a t a a t 900 ~ to 1150~ f e l l o u t s i d e t h e 2 ~ l i m i t s a t 1300~
A slightly curved line
was therefore suggested and an equation was devised
to fit i t . It w a s k n o w n t h a t s o m e d i s s o c i a t i o n of CO
h a d o c c u r r e d a t t h e h i g h e r t e m p e r a t u r e a n d it now a p pears that they may have been overoptimistic with reg a r d to t h e a c c u r a c y of t h e 1300~ d a t a . F o r t h i s
reason a simpler equation closely approximating line
A of R e f . 8 w i l l b e u s e d h e r e f o r a l l c o m p o s i t i o n s a n d
t e m p e r a t u r e s (1968 s c a l e ) w i t h i n t h e a u s t e n i t e f i e l d :

log a ~ e = -(1930/T)y~ 2 + log ( 1 - - Y C )

II) T H E y - L I Q U I D E Q U I L I B R I U M
T h e s o l i d u s l i n e of B e n z a n d E l l i o t # ~ a n d a p o r t i o n
of t h e l i q u i d u s l i n e of B u c k l e y a n d H u m e - R o t h e r y 4 c o r r e c t e d to t h e 1968 s c a l e a r e s h o w n i n F i g . 1. T h e
solidus has been given a slight inflection with downw a r d c u r v a t u r e n e a r i t s l o w e r e n d to c o n f o r m to t h e
d a t a of B a n - y a a e t a l . B o t h l h a e s a r e s u p e r i o r in a c c u r a c y to t h o s e of e a r l i e r i n v e s t i g a t o r s b u t a r e
s t r o n g l y s u p p o r t e d b y t h e e a r l i e r w o r k of A d c o c k . 2~
T h e l i q u i d u s l i n e i n c l u d e s a d o t t e d e x t e n s i o n to t h e
c a l c u l a t e d ~7 m e l t i n g p o i n t of y - F e . I n t e r p o l a t e d v a l u e s
a r e l i s t e d i n T a b l e II a n d t h e e n t i r e l i q u i d u s l i n e a p p e a r s i n F i g . 4. T h e a c t i v i t y of c a r b o n a t a n y t e m p e r ature is the same at the liquidus and solidus composit i o n s . V a l u e s c a l c u l a t e d f r o m E q . [5] a r e i n c l u d e d i n
the table.

[5j
equation is:

Table I. Solubility o f G r a p h i t e and C e m e n t i t e in A u s t e n i t e

Graphite
Temp, ~
727*
738t
800
900
1000
1100
1148~
115482

1495~

1400 ~ 9 4 o

,oo

+7

zo ~

"

./~f11141

"8
~ llO0--

/'2"

~-iooo

Pct C

YC

Pct C

0.0320
0 0408
0.0561
0 0725
0 0896
0 0990

0.68
0 87
1.19
1.53
1 89
2.08

0 0356

0.77
0.94
1.22
1.55
1.92
2.11
-

56-VOLUME 3, JANUARY 1972

Cementlte

YC

*Cement]te eutectold.
#Graphite eutectoid.
$Cementlte eutectm.
82Graphite eutectic.

I
,5

(Auste mte )

log [ y c / ( 1 - y c )]

T h e a c t i v i t y of i r o n , b y t h e G i b b s - D u h e m

!
+

1558 ~

m27~~
1500

log a ~ = 2 3 0 0 / T - 0 . 9 2 0 + (3860/T)y C

[6]

T h e s o l u b i l i t y of g r a p h i t e i n a u s t e n i t e i s r e a d i l y c a l c u l a t e d f r o m E q . [5J b y s e t t i n g a ~ e q u a l to u n i t y . T w o
o t h e r k i n d s of d a t a a r e a l s o a v a i l a b l e : t h e d i r e c t m e a s u r e m e n t s of W e l l s 2a a n d of G u r r y 24 a n d a d o w n w a r d
e x t r a p o l a t i o n of t h e s o l i d u s l i n e of B e n z a n d E l l i o t # a
to t h e e u t e c t i c t e m p e r a t u r e . A l l of t h e s e d a t a a r e i n
rather good agreement and average values are shown
i n T a b l e I. F o r c o n v e n i e n c e t h e d a t a o n s o l u b i l i t y of
c e m e n t i t e a r e i n c l u d e d b u t a d i s c u s s i o n of t h e s e a n d
of t h e a - y b o u n d a r y w i l l b e d e f e r r e d to l a t e r s e c t i o n s .
B o t h s o l u b i l i t y t i n e s a r e s h o w n i n F i g . 1.

0.0442
0.0580
0.0730
0.0910
0 1000
-

///

9115 ~

oo\

//

800 -d+ T ~
///76r - .... :f,-~'
_ : =,~~6,"*%7
8 / , ~ .'
.

T + Fe3 C

700 -a~
0

I
05

0 77

I
I
I0
I5
Corbon Weight Percent

I
20

23

cl c\,
727*

Fig. 1--Portion of the phase d i a g r a m Fe-C. Metastabie Yrange and s y s t e m Fe-Fe3C shown by dashed lines. Curie t e m p e r a t u r e dotted.
METALLURGICAL TRANSACTIONS

Table II. Solid-Liquid

Equilibria

o =__--) __. ,,-,

,oo.

7-Solidus
Temp, ~

__..

2-JJ.z-

Liquidus

Pct C

YC

ac

Pct C

YC

2.11
2.08
1 85
1 59
1.30
1.01
0.71
0.42
0 17
0 O0
.

0,1000
0.0990
0.0877
0.0718
0.0613
0.0475
0.0333
0.0196
0.0079
0.0000

1 000
0.720
0.457
0.323
0.203
0 117
0 057
0.019
0.000

4.30
4.26
3.93
3.50
3.02
2.47
1.88
1.21
0.53
0.00
.

0,2092
0 2072
0.1906
0.1689
0.1450
0.1179
0.0891
0.0570
0,0248
0.0000

1148"
11541"
1200
1250
1300
1350
1400
1450
1495:~
152782
1538w

*Cementge eutectlc.
tGraphlte eutecnc.
:~Pentecttc. The valueofa c is an averagefrom Eqs. [5] and [7].
~IMetastable meltingpoint of 7-Fe.
wMelting point of 8-Fe

06

0403-

I ~L&I200*C

-o

///~

-;-~

o z -

o" 0 , -

/ / /

""

[660

,760
-

.;.;

j/ // /
++>-"

-030

~,

o I

o 2

Yc
Fig. 2--Activ'ity coefficient of carbon in liquid iron. Lines Eq.
[7]. A graphite solubility; + gas equilibrium; [] points on
tiquidus.

III) T H E L I Q U I D P H A S E
T h e a c t i v i t y of c a r b o n in liquid F e - C a l l o y s h a s
b e e n d e t e r m i n e d by a n u m b e r of i n v e s t i g a t o r s u s i n g
s e v e r a l m e t h o d s . T h e b e s t a c c u r a c y has b e e n
a c h i e v e d by R i c h a r d s o n and D e n n i s 26 u s i n g t h e e q u i l i b r i u m of E q . [2J. It is k n o w n that s e r i o u s e r r o r s
o c c u r at high c a r b o n c o n t e n t and the p r e c i s i o n of the
d a t a i m p r o v e s a s the c a r b o n c o n t e n t and the CO c o n t e n t of the g a s d e c r e a s e . T h e i r e x p e r i m e n t a l t e m p e r a t u r e s (48) w e r e 1560 ~ 1660 ~ and 1760~
For lower
t e m p e r a t u r e s I h a v e u s e d t h e a c t i v i t y in a u s t e n i t e at
p o i n t s a l o n g the s o l i d u s , T a b l e II, to d e t e r m i n e the
a c t i v i t y c o e f f i c i e n t in the l i q u i d f o r c o m p o s i t i o n s
a l o n g the l i q u i d u s . F o r h i g h e r c o n c e n t r a t i o n s t h e
s o l u b i l i t y of g r a p h i t e f u r n i s h e s a s e c u r e b a s e w h e r e
a C = 1. U s i n g t h e s e d a t a j and a d o p t i n g the f o r m of
E q . [4], I h a v e o b t a i n e d t h e e q u a t i o n : ~
log a~ = l 1 8 0 / T - 0.870 + (0.72 + 3 4 0 0 / T ) y C
+ log [ y c / ( 1 - Y c ) ]

[7]

It w a s s h o w n that t h i s e q u a t i o n a g r e e s f a i r l y w e l l w i t h
t h a t of B a n - y a e t a l . ~ w h e r e l i q u i d and s o l i d d a t a c o u l d
be c o m p a r e d . T h e a g r e e m e n t w i t h E q . [5] is d i s t i n c t l y
b e t t e r a s s h o w n in F i g . 2 w h e r e the p o i n t s m a r k i n g
METALLURGICAL TRANSACTIONS

o~

// ~ ~ /
l/

~ -I
--

L,qo,a

-~ol g
005

~2"
2 1
0

I%C
I

302
2%

3'/o

II

OI

4"/,,

5~

',)

02

6~
0

30~

YC
Fig. 3--Activity of carbon in 7 and liquid iron. Standard state
is graphite.

/
~.jsoo
x:f / ~oOseo

o 5

the l i q u i d u s h a v e b e e n c a l c u l a t e d f r o m the a c t i v i t y in
the s o l i d . At the p e r i t e c t i c the a c t i v i t y of c a r b o n in
the s o l i d by E q . [5] is 0.0199 w h i l e in the l i q u i d by
E q . [7] it is 0.0185. The d i s c r e p a n c y is n e g l i g i b l e
s i n c e it is e q u i v a l e n t to an e r r o r of l e s s than 0.01 pct
C in the p e r i t e c t i c a u s t e n i t e . A c c o r d i n g l y the a c t i v i t y
at the p e r i t e c t i c is t a k e n a s 0.019 0.001.
A s u m m a r y of t h e a c t i v i t y of c a r b o n in a u s t e n i t e
and in l i q u i d i r o n is g i v e n in F i g , 3. T h e c h e m i c a l p o t e n t i a l of c a r b o n m a y be r e a d a s PC - tt~ = 4 . 5 7 5 T
x log a c . T i e l i n e s in the t w o - p h a s e f i e l d a r e s h o w n ,
A line f o r c e m e n t i t e would be a l m o s t i n d i s t i n g u i s h a b l e
on t h i s s c a l e f r o m the g r a p h i t e l i n e at log a c = 0, It
would lie s l i g h t l y a b o v e t h i s l i n e at a l l t e m p e r a t u r e s
b e l o w the e u t e c t i c .
T h e a c t i v i t y of i r o n in the l i q u i d a s found by the
Gibbs-Duhem equation is:
log a/Fe = --(0.36 + 1700/T)y~

+ log (1 - y c )

[8]

It has b e e n s h o w n 27 that this a g r e e s w i t h the d a t a of

Syu, P o l y a k o v , and S a m a r i n 28 at 1560~
T h e s o l u b i l i t y of g r a p h i t e in l i q u i d i r o n has b e e n
m e a s u r e d by m a n y i n v e s t i g a t o r s . Up to 1800~ e x c e l l e n t a g r e e m e n t is found a m o n g the d a t a of R u e r and
B i r e n , 29 C h t p m a n , A l f r e d , G o t t e t a l . , 3~ and of Kitch=
e n e r , B o c k r i s , and S p r a t t . 3~ D a t a up to 2500~ w e r e
r e p o r t e d by R u e r and B i r e n , up to 2875~ by C a h i l l ,
K i r s h e n b a u m , and G r o s s e 32 and at 2050 ~ to 2375~ by
Y e r t m a n , G r i g o r o v i c h , N e d u m o v , and S a m a r i n . 33 A v e r
a g e d v a l u e s a r e s h o w n in F i g . 4; i n t e r p o l a t e d data to=
g e t h e r w i t h e s t i m a t e s of p r o b a b l e a c c u r a c y a r e g i v e n
in T a b l e III. T h e s e l e c t e d e u t e c t i c at 1154~ and 4.26
+ 0.02 p c t C has b e e n c o n f i r m e d by R u t h and T u r p i n 34
who r e p o r t 4.28 + 0.02 and 4.32 0.03 r e s p e c t i v e l y
f o r the F e - C and F e - F e 3 C e u t e c t i c s .
T h e n o r m a l b o i l i n g point of i r o n (68) a c c o r d i n g to
H u l t g r e n , O r r , A n d e r s o n , and K e l l e y 3s is 2870~
The
e f f e c t of c a r b o n on the v a p o r p r e s s u r e m a y be c a l c u l a t e d on t h e b a s i s of E q . [81 f o r t e m p e r a t u r e s up to
1800~
A t h i g h e r t e m p e r a t u r e s the s o l u b i l i t y of
g r a p h i t e i n c r e a s e s m o r e r a p i d l y , r e s u l t i n g in a s o m e what l o w e r e d a c t i v i t y c o e f f i c i e n t . M a k i n g a l l o w a n c e
f o r t h i s e f f e c t , the b o i l i n g p o i n t s of a l l o y s and t e m p e r a t u r e s at w h i c h the v a p o r p r e s s u r e r e a c h e s 0.1
and 0.01 a i m h a v e b e e n c a l c u l a t e d a n d the r e s u l t s a r e
s h o w n in F i g . 4.
VOLUME 3. JANUARY 1972-57

~ooo ~
~
: :PFe
' : - -=- I- otm
----

900

BoLhng point

250C -- PFe = 0 I arm

800

200O

PFe = 0 0 l otm
~83 ~

~+7

(D

~, 7O0
E

i38~

~15oo

L * Fe3C

i I

d + C
or G + Fe3C

12270

(I)
o-

~ )

#-mooo

H54~

T+C
or T Fe3C

600
FI
!
!

738~
727 ~

5ool--

o:. c

~_

_L-

-.

Carbon percent in ~Z-Fe

Fe~

2--3o_~ . . . . . . . . . . . . .

l o.& o& o.&

or e'+ F % C

OI
Fez

4
5
6
7
8
9
Corbon Weight Percent

IO

II

12

0 2

0.5 0.4
0 5
0.6
0 7
Carbon percent m 7-Fe

0.8

0.9

Fig. 5--Equilibria involving c~-ferrite. Metastable system F e F%C shown by dashed lines.

Fig. 4--The Fe-C phase diagram.

Table II1. Solubility of Graphite in Liquid Iron

Temp, ~

Carbon, Wt Pct

1154
1200
1300
1400
1500
1600
1700
1800
1900
2000
2100
2200
2300
2400
2500
2600
2700
2800
2900

4 26 0 02
4.37
4.63
4.88
5.14
5.40 0.03
5.66
5 94 0.05
6.26 0 10
6.63 0 10
7.05
7.56 0.3
8.1
8.68
9.28 0.4
9.87
10.50
11.12
11.75 0.5
IV) THE

5-PHASE

AND

PERITECTIC

The melting point of 5-Fe according to Boulanger 3~

adjusted to the 1968 scale is 1538~
The metastable
melting point of F-Fe is found from thermal data 17 to
be 1527~
The 7-5 inversion for pure Fe 3~ is 1394~
Fig. 1 shows the 5-Fe region with the peritectic at
1495~
(68) as recommended
by Buckley and HumeRothery. 4b The 5 liquidus also depends on these
authors. It is shown as a straight line from the melting point to 0.53 pct C at the peritectic. The 5-solidus
also is based on results of the above investigators.
The compositions of the peritectic are 5, 0.09 pct C;
7, 0.17 pct C; liquid, 0.53 pct C.
58-VOLUME 3, JANUARY 1972

That the above peritectic compositions selected

f r o m p u b l i s h e d p h a s e d i a g r a m s a r e in f a c t in a c c o r d
w i t h t h e l a w s of t h e r m o d y n a m i c s is shown in the f o l lowing c a l c u l a t i o n s . It has a l r e a d y b e e n s h o w n that
the a c t i v i t y of c a r b o n c a l c u l a t e d f r o m d a t a on the
l i q u i d a g r e e s w e l l w i t h that c a l c u l a t e d f r o m the s o l i d
a c = 0.019 ~= 0.001. A m o r e p r e c i s e c h e c k c a n be o b t a i n e d by c o n s i d e r a t i o n of t h e a c t i v i t y of i r o n in the
s e v e r a l p h a s e s . In the l i q u i d p h a s e t h i s i s found f r o m
E q . [8] w h i c h g i v e s log a l e = - 0 . 0 1 1 7 . T h e a c t i v i t y in
the ~ - F e p h a s e m u s t be the s a m e at e q u i l i b r i u m .
F r o m E q . [6] it is found that a t 0.17 p c t C log a y e
= - 0 . 0 0 3 5 w h e r e p u r e ~ - F e is the s t a n d a r d s t a t e . To
c o m p a r e t h e s e two v a l u e s of log a F e b o t h m u s t be r e f e r r e d to the s a m e s t a n d a r d s t a t e . T h e d i f f e r e n c e in
s t a n d a r d f r e e e n e r g y b e t w e e n l i q u i d and $ - F e f r o m
t h e t a b l e s of O r r and C h i p m a n 17 i s AC~
= 67 c a t
w h i c h c o r r e s p o n d s to a d i f f e r e n c e A log a ~ e/ of 0.0083.
T h i s , a d d e d to the v a l u e of log a T e g i v e s - 0 . 0 1 1 8 in
a g r e e m e n t w i t h the v a l u e found f o r log a/F ^ .
A similar calculation may be made for ~-Fe which
d i f f e r s f r o m ~ - F e in s t a n d a r d f r e e e n e r g y by o n l y 13
o r 14 c a l . T h i s c o r r e s p o n d s to A l o g a%-~5 = 0.0016 o r
0.0017. A d d i n g t h i s to the v a l u e log ate ~= - 0 . 0 0 3 5 we
find log aSFe = - 0 . 0 0 1 9 to - 0 . 0 0 1 8 . T h e a c t i v i t y c o e f f i c i e n t s in 5 - F e a r e unknown a n d t h e o r e t i c a l l y the a c t i v i t y of c a r b o n is p r o p o r t i o n a l to n c / ( n Fe -- n C / 3 ) .
For the small carbon concentrations considered, the
a c t i v i t y c o e f f i c i e n t of i r o n i s u n i t y and aFe = (1 - YC)"
It f o l l o w s t h a t log (1 - Y C ) is - 0 . 0 0 1 9 to - 0 . 0 0 1 8 ;
YC = 0.0044 to 0.0041 w h i c h is e q u i v a l e n t to a r o u n d e d
v a l u e 0.090 p c t C . T h e m e t h o d of c a l c u l a t i o n is m o r e
accurate than the usual "freezing point lowering" and
e m p h a s i z e s the p r e c i s i o n r e q u i r e d in f r e e e n e r g y d a t a
to m a k e a s i g n i f i c a n t c a l c u l a t i o n of a p h a s e b o u n d a r y .
T h e r e s u l t s s u b s t a n t i a t e the p u b l i s h e d t h e r m a l d a t a
METALLURGICAL TRANSACTIONS

on 6 , 7 , and liquid i r o n and indicate t h e i r c o n c o r d a n c e

with the data on the p e r i t e c t i c .
V) THE a~-}' EQUILIBRIUM
The A3 line, the composition of ~-Fe in equilibrium
with a - F e , is based almost entirely on the work of
Mehl and Wells, s6 corrected by 1~ at the pure iron
end with negligible correction at the eutectoid. The
intersections of our solubility lines place the graphite
a n d cementite eutectoids respectively at 738~ and
0.68 pct C and at 727~ and 0.77 pct C. The l a t t e r
t e m p e r a t u r e a g r e e s with a n o b s e r v a t i o n of Smith and
D a r k e n 37 and is 4~ h i g h e r than that of Mehl and W e l l s .
The s e l e c t e d line and the o b s e r v e d points of Mehl and
W e l l s a r e shown in F i g . 5.
The a - p h a s e b o u n d a r y was d e t e r m i n e d by S m i t h 2~
at 800 ~ and 750~
T h e s e data f o r m the b a s i s for the
line shown in Fig. 5 which is e x t r a p o l a t e d to 0.0206
and 0.0218 pct C at the g r a p h i t e and cemen.tite e u t e c toids. The data of S c h f i r m a n n , Schmidt, and T i l l m a n n38
i n d i c a t e a g r a p h i t e eutectoid of 0.029 pct C. The
weight of evidence however f a v o r s S m i t h ' s v a l u e .
It is r e a d i l y shown that this p o r t i o n of the d i a g r a m
is in f a i r l y good a g r e e m e n t with the t h e r m o d y n a m i c
data on a - and ~ - F e . The value of log a ~ is s i m p l y
log (1 - y ~ . To r e f e r this to a standard~setate of F e ~
we add AG~
T obtained f r o m the t a b l e s of
O r r and C h i p m a n . The c o r r e s p o n d i n g c a r b o n c o n c e n -

1400 1200
I000
I I I I
I

~C 800
I
I

600

f
5

~/~= 5550/T - 2.49

log

~7

__

t r a t i o n is then obtained f r o m Eq. [5]. Points thus c a l culated a r e shown by dots in Fig. 5. The a g r e e m e n t
m e r e l y i n d i c a t e s a f a i r l y high d e g r e e of i n t e r n a l cons i s t e n c y a m o n g the v a r i o u s data, p e r h a p s as good as
can be expected in the a b s e n c e of i n f o r m a t i o n on the
p a r t i a l m o l a r heat capacity of c a r b o n .
The s o l u b i l i t y l i n e s for g r a p h i t e and c e m e n t i t e will
be d i s c u s s e d in a l a t e r s e c t i o n .
VI) ACTIVITY AND SOLUBILITY OF GRAPHITE
IN FERRITE
The activity of carbon in bcc iron has been determined in the range 590~ to 1495~ with a wide void in
the fcc region. Since the highest concentration is 0.09
pct C, Henry's law may be assumed and a c may be
taken as proportional to either xC or YC or zC within
the precision of the data. For the activity coefficient I
shall use r
= aC/YC, the value of a C for g r a p h i t e
being taken a s unity. A plot of log ~h~ vs 104/T, shown
in Fig. 6, p e r m i t s a c o m p a r i s o n throughout the e n t i r e
r a n g e . F o r the two points of Smith on the a b o u n d a r y
the a c t i v i t y of c a r b o n is c a l c u l a t e d f r o m the ~ bounda r y at the s a m e t e m p e r a t u r e , u s i n g Eq. {5j. The value
c r e d i t e d to Scht~rmann et al.38 is t h e i r g r a p h i t e solubility at the eutectoid. At the p e r i t e c t i c t e m p e r a t u r e ,
a C is taken f r o m an e a r l i e r s e c t i o n of this p a p e r . O t h e r
p o i n t s , i n c l u d i n g one by Smith 39 at 619~ a r e b a s e d on
gas e q u i l i b r i a and the c o r r e s p o n d i n g e q u i l i b r i u m with
g r a p h i t e . In the one point of D6nwald and W a g n e r , 19 a
m o d e r n value of p C _ / p c ~ for g r a p h i t e has b e e n substituted for the e r r ~ n e o u ~ v a l u e a c c e p t e d in 1931.
Other data a r e as r e p o r t e d by t h e i r a u t h o r s . The
plotted data of Swartz 9 include only those b a s e d on
c o m b u s t i o n a n a l y s i s of c a r b o n . The s t r a i g h t line
b a s e d on the a s s u m p t i o n that ACp = 0 has the equation:

log ~

= 5550/T - 2.49

[9]

which c o r r e s p o n d s to a heat of s o l u t i o n of g r a p h i t e ,
AH = 25.40 k c a l , a value l a r g e r than was p r e v i o u s l y
accepted. Below the graphite eutectoid, Eq. [9J may
be solved for the s o l u b i l i t y of g r a p h i t e (a c = 1). Exp r e s s e d in p a r t s p e r m i l l i o n , with a slight a d j u s t m e n t
to a g r e e with Fig. 5, this gives for the s o l u b i l i t y of
graphite:

log [C]a ppm = 7.81 - 5550/:s

The indicated graphite solubilities are shown in Table

IV. It should be mentioned that while the data seem
fairly concordant some uncertainty remains concerning Smith's residual inactive carbon and Swartz's
mysterious " t r a p s " for carbon in 6-Fe.

"~ Smtth 1962

~7 Dunwold and Wagner
n Swartz
X Sch'(irrnonn el el
0 Perltectic, ~-Fe

/
/
/
I

[i0]

VII) THE IRON CARBIDES

'%
D

,O"/z

I0

II

12

Fig. 6--Activity coefficient of carbon in t~-6-iron. The standard state is graphite; ~C= a~/v,-,.
METALLURGICALTRANSACTIONS

Numerous carbides of iron are reported in the

chemical and metallurgical literature ranging in composition from FeC to Fe4C. Only two of these have
been studied under metastable equilibrium conditions
and it is only for these two that thermodynamic data
a r e available.
Cementite is usually assigned the formula Fe3C but
its exact conformance to the stoichiometric composition has not been proved and variations in composition
have been suggestedfl Petch4~quenched carbide-saturated alloys from various temperatures and found that

VOLUME 3, JANUARY 1972-59

200

Table IV. Solubility of Graphite and Carbides in <~-Fe

O--

Parts per mdhon

Temp,

738
727
700
650
600
550
500
450
400
350
300
250
200

Graphite*

Fe3Ct

Fe:.2C :~

206

~.--~
~'0~"

-zoo-

" ~ ~

et

Schell

ol

~. Smith (mterpolo~ed~
[:] Eutectlc
___ _

--

So,ub,,,,.
,y,~-F~

-400

127
63
28
11 7
4.3
1 35
0 37
0 081
0,013

218
160
102
57
28
13
5.7
2.3
0 75
0.21
0.045
0.007

'~ - 8 0 0
-I000

1.3
0.30
0 050
0.0055

*Derived from Fig. 6

tCalculated from observed value at 727~ and free energy of formahon.
$From free energy of formation.

the l at t i ce p a r a m e t e r of the c e m e n t i t e v a r i e d with

quenching t e m p e r a t u r e . O t h e r o b s e r v e r s have r e p o r t e d s i m i l a r d i f f e r e n c e s . 4~'42 The s t r u c t u r e is o r t h o r h o m b i c and the C u r i e t e m p e r a t u r e is a p p r o x i m a t e l y 210~ with v a r i a t i o n s dependent upon the
p r e v i o u s h i s t o r y . It is s o m e t i m e s c a l l e d 0 (theta)
carbide.
The p o s s i b l e e x i s t e n c e of Fe2C was s u g g e s t e d by
Glud, Otto, and R i t t e r . 4~ An X - r a y d i f f r a c t i o n p a t t e r n
of Hofmann and G r o l l 4z f o r i r o n c a r b u r i z e d at t e m p e r a t u r e s below 400~ showed lines of an unknown c a r bide along with t h o s e of Fe3C. When c a r b u r i z a t i o n
was done above 400~ only the l a t t e r was found. B a h r
and J e s s e n 43 d e v e l o p e d a h y d r o g e n - r e d u c t i o n m e t h o d
f o r independent d e t e r m i n a t i o n of c a r b i d i c and f r e e
c a r b o n . With its a i d they w e r e able to show that
when i r o n , r e d u c e d f r o m oxide by h y d r o g e n at about
260~ was c a r b u r i z e d with CO at 225~ the p r o d u c t
contained 9.7 pct C c o r r e s p o n d i n g to FezC. At h i g h e r
c a r b u r i z i n g t e m p e r a t u r e s a m i x t u r e of FezC and
Fe3C was f o r m e d and at 400~ or above the c a r b i d i c
c a r b o n c o r r e s p o n d e d to the f o r m u l a Fe3C. T h e X - r a y
d i f f r a c t i o n p a t t e r n of this new c a r b i d e was d e t e r m i n e d a y e a r l a t e r by Hgigg44 and it is g e n e r a l l y c a l l e d
the H~gg c a r b i d e o r X (chi). J a c k 4s obtained the s a m e
c a r b i d e by c a r b u r i z a t i o n of the n i t r i d e . Its a n a l y s i s
showed a slightly v a r i a b l e c o m p o s i t i o n a p p r o x i m a t i n g
Fee.eC.
Cementite, O
Twenty y e a r s ago D a r k e n and G u r r y 46 r e v i e w e d the
p r o p e r t i e s of c e m e n t i t e and d e v e l o p e d t a b l e s of its
t h e r m o d y n a m i c p r o p e r t i e s . They w e r e a b l e to show
that Fe~C is m e t a s t a b l e at a ll t e m p e r a t u r e s with r e sp ect to g r a p h i t e and its s a t u r a t e d solution in i r o n .
Thus they p r o d u c e d the f i r s t m o d e r n p h a s e d i a g r a m
of the s y s t e m ; a l l s u b s e q u e n t d i a g r a m s , including the
p r e s e n t , have added only r e f i n e m e n t in d e t a i l .
The line in F i g . 1 r e p r e s e n t i n g the s o l u b i l i t y of c e m e n t i t e in a u s t e n i t e is taken f r o m the p a p e r by B a n ya, e t a l . e and is b a s e d on the d i r e c t m e a s u r e m e n t s of
solubility by Smith ~7 and the CO-CO2 e q u i l i b r i u m
m e a s u r e m e n t s of S c h e i l e t a l . 7 With the a i d of E q s .
[5] and [6] i n t e r p o l a t e d points f r o m t h e s e data and a
60-VOLUME

I
0

3, J A N U A R Y 1 9 7 2

-1200
I000

Fig. 7--Standard

I
I100

I
l
1200
Tempereture,

free energy

]
1300

1
1400

Kelvin

of the reaction

3 Fe(-/) + C ( g r a p h -

ite) = Fe3C. Assumed formula: FesC.

point c a l c u l a t e d f r o m the e u t e c t i c c o m p o s i t i o n have
been u s e d to e s t a b l i s h the s t a n d a r d f r e e e n e r g y change
in the r e a c t i o n :
3 Fe(7) + C( g r ap h i t e) = Fe3C(equilib.)

[11]

The r e s u l t is shown in F i g . 7. The c u r v a t u r e is s o m e what g r e a t e r than is o r d i n a r i l y e x p e c t e d in a plot of

this kind. U n c e r t a i n t y r e m a i n s a s to w h e t h e r this is
to be a s c r i b e d to a change in heat c a p a c i t y in the r e a c tion o r to v a r i a t i o n s in c o m p o s i t i o n of the c e m e n t i t e
p h a s e , o r to e x p e r i m e n t a l e r r o r . A s s u m i n g the f i r s t ,
a value of A C p = --3.4 cal. deg -1 mo1-1 could be u s e d
to r e p r o d u c e the o b s e r v e d c u r v a t u r e in the r a n g e
1000 ~ to 1421~
H o w e v e r it w i l l be p r e f e r a b l e to r e t u r n to t h i s q u e s t i o n a f t e r c o n s i d e r a t i o n of the s o l u bility of Fe3C in c~-Fe.
The o b s e r v e d f r e e e n e r g y and heat of f o r m a t i o n at
the e u t e c t i c p r o v i d e a b a s i s f o r c a l c u l a t i o n of the s o lubility of c e m e n t i t e in liquid i r o n . The o t h e r data
r e q u i r e d a r e the a c t i v i t i e s of i r o n and c a r b o n in the
liquid by E q s . [7] and [8] and the f r e e e n e r g y d i f f e r ence ~7 b e t w e e n 7 and liquid i r o n . T h e r e a r e no e x p e r i m e n t a l data on this p r o b l e m and no m e a s u r e m e n t s of
the m e l t i n g point. V a r i o u s e s t i m a t e s have been m a d e
including a r e c e n t one by H i l l e r t . 48 The r e s u l t of the
c a l c u l a t i o n is a v e r y flat m a x i m u m shown by a dotted
line in F i g . 4, and a c a l c u l a t e d m e l t i n g point of 1227~
At l o w e r t e m p e r a t u r e s t h e r e a r e two d i s t i n c t and
c o n f l i c t i n g l i n es of e v i d e n c e on the f r e e e n e r g y of f o r mation of Fe3C f r o m c~-Fe and g r a p h i t e . The a c t i v i t y
of c a r b o n as shown by F i g . 6 o r Eq . [9] can be u s e d to
c a l c u l a t e the f r e e e n e r g y f r o m the o b s e r v e d s o l u b i l i t y .
It happens that the solubility is quite s m a l l and the
data c o n f l i c t i n g . M o r e o v e r the s o l u b i l i t y m ay be a f f e c t e d by p r e c i p i t a t i o n s t r e s s e s a s shown by Swartz.9
His m o r e r e c e n t o b s e r v a t i o n s on s e l f - s t r e s s e d and
s t r e s s - f r e e c e m e n t i t e m u s t be r e g a r d e d a s s u p e r s e d ing the e a r l i e r work by the s a m e t e c h n i q u e , d e t e r m i n at i o n of the Snoek peak in the i n t e r n a l f r i c t i o n s p e c t r u m . It a p p e a r s 9b that with l o n g e r aging the p r e c i p i t at ed c e m e n t i t e has about the s a m e solubility as the
s t r e s s - f r e e . The f r e e e n e r g y c a l c u l a t e d f r o m the
s o l u b i l i t y data is shown, along with o t h e r d e t e r m i n a t i o n s , in F i g . 8.
M o r e d i r e c t i n f o r m a t i o n on c e m e n t i t e c o m e s f r o m
s t u d i e s of the e q u i l i b r i u m ,
Fe3C + 2Ha = 3 Fe(a) + CH4
METALLURGICAL

[12]
TRANSACTIONS

+4

"~,.~"~-"'~
__
~ ' v \
~+2-",c

, 1

600

"',

",,,
0~'~,,

[] FesC Wotase
A FesC Browning et al
---FesC Swartz solubility
O FesC From T-Fe data
V Fe2C ( Browning

~,~
,

o~

-I-

800
1000
Temperature, Kelwn

1200

3Fe(a) + C(gr) = F%C

ar~
1400

Fig. 8--Standard free e n e r g y of formation of FesC(0) and

Fe2.2C(x ) f r o m a - F e and graphite.

and the known f r e e e n e r g y of m e t h a n e . The e q u i l i b r i u m

w a s s t u d i e d in t h e r a n g e 725 ~ to 875~ by W a t a s e 49 a n d
at l o w e r t e m p e r a t u r e s by B r o w n i n g , DeWitt, and E m m e t t . 5~ T h e l a t t e r i n v e s t i g a t o r s d r e w s e p a r a t e l i n e s
t h r o u g h t h e two s e t s o f r e s u l t s a n d c o m p u t e d t h e f r e e
e n e r g y a n d h e a t of f o r m a t i o n . T h e l a t t e r , t h o u g h
p o o r l y d e t e r m i n e d by t h e d a t a , h a s b e e n w i d e l y

quoted. It is now possible to improve on this treatment by consideration of the data at higher temperatures, Fig. 7, and the thermal properties of the reacting species. This was done by Darken and Gurry 4~
with whose results the following calculations are in
good agreement.
The data points corresponding to the
observed methane equilibrium are shown in Fig. 8.
The high-temperature
data of Fig. 7 are easily recalculated using the free energy differences tabulated
by Orr and ChipmantT~to show the free energy of formation from metastable ~-Fe. The results are shown
in Fig. 8. "In order to establish the thermodynamic
properties from these data it is first necessary to examine the data on the enthalpy and entropy of FeaC.
At low temperatures
(68 ~ to 298~
the heat capacity
was determined by Seltz, McDonald, and Wells 51 whose
value for S~gs was 25.7 + 1.0. From this and data of
Schwarz and Ulich 5e and Naeser, ~3 Kelley and King 54
proposed an average value of S~98 = 24.2 i 1.0. More
recent measurements
by Mazur and Zacharko 55 have
covered the range 2 ~ to 20~ thus filling part of the
uncertainty in Seltz's estimate of the entropy. A recalculation of Seltz's data made very little change in
his original figure but probably improved its overall
reliability. The high-temperature
data on free energy
shown in Figs. 7 and 8 are better fitted by the value
S~%8 = 25.00. This value, which lies well within the
range of uncertainty, is adopted for the calculations
and tables.
Estimates of the thermodynamic
properties of Fe3C
at high temperatures
are based principally on the
measurements
of Naeser 53 and Umino.56 The latter
were recalculated by Darken and Gurry 46 and included
in their tabulated enthalpy data. Corresponding
values
of the free energy function came from the entropy and
equilibrium data mentioned above. Kelley ~7 used the
s a m e d a t a p l u s S c h w a r z a n d U l i c h ~2 to a r r i v e a t a
similar tabulation.
It i s now p o s s i b l e to m a k e s o m e n u m e r i c a l a d j u s t m e n t in t h e d a t a to c o n f o r m m o r e c l o s e l y w i t h t h e d i r e c t l y d e t e r m i n e d d a t a o n t h e f r e e e n e r g y of f o r m a METALLURGICAL TRANSACTIONS

Table V. Thermodynamic Properties of Cementite, Fe s C

H T - H s t ST-Sst

T,~

Cp

298.15
400
450
480*
500
600
700
800
850
900
950
1000

25.40
27.93
29.98
30.71
26.50
27.20
27.90
28.60
28.95
29 30
29.65
30.00

0
2710
4140
5052
5624
8309
11064
13889
15328
16784
18258
19749

0.00
7.80
11 21
13.17
14.34
19.23
23.48
27 25
28.99
30.65
32.34
33 78

S~

AG~

AH}

AS~-

25.00
32.80
36.21
38.17
39.34
44.23
48.48
52.25
53 99
55 65
57.24
58.78

4772
4274
3949

5985
6534
6802

4 07
5 65
6 34

3618
2916
2214
1524
1192
885
585
300

7083
7176
7121
6892
6692
6411
6019
5450

6.93
7 10
7.0l
6 71
6.47
6 14
5 72
5.15

*Curm temperature.

700" 600
500
I I I I
I
2 ~
E

400
I

500
I

2001000/

100

10

o_

Fe2C (X)

u
--

C
o

Grophlte ~

C,)

-2

001

-5

0001

-4

10

I
II

I
12

I
1:5

i
14

I
15

I
16

I
17

[
18

I
19

I
20

"1,,, 00001
21

I&/T
Fig. 9--Solubilities in a-Fe; line for (Fe2.2C) and solid line
for FeaC f r o m f r e e energy data.
lion. The s e l e c t e d values s h o w n in T a b l e V a r e b a s e d
p r i m a r i l y o n t h e e q u i l i b r i u m d a t a a t 500 ~ to 700~ a n d
t h e s o l u b i l i t y in ~ - F e at 1000~
T h e l i n e in F i g . 8 r e r e p r e s e n t i n g t h e f r e e e n e r g y of f o r m a t i o n of F e s C
f r o m c ~ - F e f o l l o w s t h e t a b u l a t e d v a l u e s up to 1000~
C o r r e s p o n d i n g v a l u e s f o r i t s s o l u b i l i t y in a - F e a r e
s h o w n in F i g . 9. T h e s e lie s l i g h t l y b e l o w t h e l i n e o b tained by S w a r t z f r o m i n t e r n a l f r i c t i o n m e a s u r e m e n t s
and d e c i d e d l y below e a r l i e r values by that m e t h o d .
The line m a y be r e p r e s e n t e d by the equation f o r the
s o l u b i l i t y of F e s C
log [C] c~ p p m = 6.38 - 4 0 4 0 / T

[13]

w h i c h c o r r e s p o n d s to a h e a t of s o l u t i o n of c e m e n t i t e ,
AH = 18.47 k c a l . T h i s i s to b e c o m p a r e d w i t h 24.0
kcal from Swartz's data.
B o r e l i u s a n d B e r g l u n d s8 m e a s u r e d t h e h e a t e v o l v e d
on p r e c i p i t a t i o n of c e m e n t i t e f r o m c~-Fe w h i c h had
b e e n e q u i l i b r a t e d a t t e m p e r a t u r e s o f 350 ~ to 700~
and from the results calculated the solubility. Their
r e s u l t s a t 700~ a r e l o w e r t h a n t h o s e o f S w a r t z o r of
S m i t h o r of E q . [13] a n d t h e i r h e a t of s o l u t i o n w a s
o n l y 12.5 k c a l p e r g - a t o m of c a r b o n . A t 500 ~ to 600~
t h e i r v a l u e s a g r e e w i t h t h e c a l c u l a t e d c u r v e of F i g . 9
w h i l e a t l o w e r t e m p e r a t u r e s t h e y a r e m o r e n e a r l y in
line with the data of S w a r t z .
T h e c u r v a t u r e in t h e line f o r t h e f r e e e n e r g y of
F e s C s h o w n in F i g . 7 m a y now b e r e c o n s i d e r e d . T h i s
i s not to b e b r u s h e d a s i d e a s e x p e r i m e n t a l e r r o r s i n c e
VOLUME 3, JANUARY 1972-61

it is b a s e d on c l o s e l y a g r e e i n g i n v e s t i g a t i o n s which
in a l l o t h e r r e s p e c t s have been w e l l - s u b s t a n t i a t e d . It
was shown that the c u r v a t u r e could be a c c o u n t e d f o r
by a heat c a p a c i t y change in the r e a c t i o n of ACp = - 3 . 4
c a l p e r deg m o l e . T h i s would m a k e its m o l a r heat
c a p a c i t y at 1200~ about 26.4 c a l p e r deg. In view of
T a b l e V only an a b r u p t change at 1000~ could lead to
s u c h a low value. It is to be r e m e m b e r e d that the
s t a n d a r d f r e e e n e r g y of f o r m a t i o n shown in F i g . 7 is
b a s e d on the a s s u m p t i o n that the c o m p o s i t i o n is Fe3C.
V a r i a t i o n s f r o m this c o m p o s i t i o n could be e x p e c t e d to
a f f e c t the t h e r m o d y n a m i c p r o p e r t i e s . At the p r e s e n t
t i m e , h o w e v e r , no q u a n t i t a t i v e explanation of the c u r v a t u r e can be o f f e r e d . F u r t h e r r e s e a r c h on this q u e s t i o n
is c l e a r l y n eed ed .
In Fig. 7 a point is shown at 1000~ w h i c h is c a l c u lated f r o m the s o l u b i l i t y of c e m e n t i t e in a - F e and the
known f r e e e n e r g y d i f f e r e n c e b e tw e e n a - and y - F e .
A s t r a i g h t line f r o m this point to that c a l c u l a t e d f r o m
the e u t e c t i c at 1421~ is r e p r e s e n t e d by the e q u a t i o n
3 Fe(v) + C ( g ra p h it e ) = Fe3C

AC} = 2 6 8 5 - 2.625T

[14]

This approximate equation reproduces the data within

+60 cal and should serve well enough for practical
purposes until a better knowledge of the composition
of cementite is available.
T h e H~gg C a r b i d e ,
B ro wn i n g , DeW it t, and E m m e t t 5~ also m e a s u r e d the
equilibrium
Fe2C + 2H2 = 2 F e ( a ) + CH4

[15]

in the t e m p e r a t u r e r a n g e 296 ~ to 359~

Their carbide
was p r e p a r e d by t r e a t m e n t of h y d r o g e n - r e d u c e d i r o n
with butane at 275~ and was identified by its d i f f r a c tion p a t t e r n as the s a m e as that p r e p a r e d by H~gg at
225~
Both o b s e r v e r s found that this c a r b i d e was
c o n v e r t e d to Fe3C by heating to 500~
J a c k 45 obtained the s a m e c a r b i d e which he c a l l e d
Fe20Cg. The X - r a y p a t t e r n was indexed as o r t h o r h o m b i c with the a d d e d notation that a m o n o c l i n i c o r
t r i c l i n i c s t r u c t u r e was not excluded. M o r e r e c e n t l y
it was shown by SCnateur, F r u c h a r t , and M i c h e l s9 that
the s t r u c t u r e is m o n o c l i n i c and isotypic with MnsC2.
F o r p u r p o s e s of the p r e s e n t d i s c u s s i o n it is r e p r e s e n t e d as Fe2.2C. Its C u r i e t e m p e r a t u r e is g i v e n by
H o f e r 6~ as 247~
A v e r a g e e q u i l i b r i u m values of Browning et al. f o r
E q . [15J a r e shown in F i g . 8. The slope of the line is
not w e l l - d e f i n e d but the data a r e r e p r e s e n t e d a p p r o x i m a t e l y in the equation:
2.2 F e ( a ) + C ( g r a p h i t e ) = Fe2.2C(
AG ~ = 4850 - 2 . 5 T

[16J

E x t r a p o l a t i o n to l o w e r t e m p e r a t u r e s i n d i c a t e s that
X b e c o m e s a m o r e s t a b l e phase than Fe3C at t e m p e r a t u r e s below about 500~
The t r i p l e point X-O-or is
not a c c u r a t e l y d e t e r m i n e d by the data. K r i s e m e n t , 6~
using the method of B o r e l i u s and B e r g l u n d , 5~ found
that the p r e c i p i t a t e f o r m e d at 230~ was c e m e n t i t e
w h e r e a s at 188 ~ to 218~ a d i f f e r e n t c a r b i d e which he
c a l l e d Fe2C a p p e a r e d . T h e c a u s e of the b r e a k in his
c u r v e r e m a i n s o b s c u r e . J a c k found that p e r s i s t e d
62-VOLUME 3, JANUARY 1972

f o r 50 hr at 350~ but was c o n v e r t e d to c e m e n t i t e at

450~
L e s a g e B2 r e p o r t e d the f o r m a t i o n of only at
230 ~ to 450~
It is difficult to d i s t i n g u i s h t h e r m o d y n a m i c f r o m k i n e t i c e f f e c t s but t h e r e would s e e m to be
the p o s s i b i l i t y that the c r o s s - o v e r point is s o m e w h a t
h i g h e r than the 500~ i n d i c a t e d .
The c C a r b i d e
A n o t h e r w e l l - d e f i n e d c a r b i d e , ~ (epsilon) o c c u r s
as a t r a n s i t i o n p h ase in the t e m p e r i n g and aging of
s t e e l . It has not been i s o l a t e d and i t s t h e r m o d y n a m i c
p r o p e r t i e s a r e unknown. It is d e s c r i b e d 6~ as hcp with
a C u r i e t e m p e r a t u r e of 370~ and a v a r i a b l e c o m p o s i tion, c o m m o n l y about Fe2.4C. It was r e c o g n i z e d by
J a c k 83 a s a r e s u l t of the t e m p e r i n g of m a r t e n s i t e and
by T s o u , Nutting, and M e n t e r 64 in the q u e n c h - a g i n g
of i r o n . The voluminous and co n f u si n g l i t e r a t u r e on
t h e s e p h e n o m e n a contains l i t t l e on which an e s t i m a t e
of its f r e e e n e r g y can be b a s e d . B u t l e r , C h o l l e t , and
C r u s s a r d 65 e s t i m a t e d its a p p a r e n t s o l u b i l i t y in a - F e
f r o m the shape of the aging c u r v e and p r o p o s e d the
formula
% C a = 1.15 exp [-6100/RT]

[17]

This would m a k e its s o l u b i l i t y a t h o u s a n d - f o l d g r e a t e r

than that of e i t h e r of the o t h e r c a r b i d e s . A r n d t and
D a m a s k 68 m e a s u r e d the e n e r g y r e l e a s e d in the f o r m a tion of the m e t a s t a b l e c a r b i d e p r e c i p i t a t e and r e p o r t e d
this as 0.27 ev p e r c a r b o n a t o m . T h i s is e q u i v a l e n t to
6200 c a l in r e m a r k a b l e a g r e e m e n t with the va l ue e s t i m a t e d f r o m the s o l u b i l i t y . T h i s a g r e e m e n t s u g g e s t s
an e q u a t i o n f o r the f r e e e n e r g y of f o r m a t i o n of the p r e c i p i t a t e . T h i s is not a " s t a n d a r d " f r e e e n e r g y s i n c e
it i g n o r e s the e f f e c t s of p a r t i c l e s i z e and p r e c i p i t a t i o n
strain.
2.4 F e ( a ) + C ( a ) = Fe2.4C(s p r e c i p i t a t e )

[18]

log [C] a (ppm) = 4.06 - 1335/T

AG (ppm) = --6100 + 4.27 T
SUMMARY
A c r i t i c a l r e v i e w of p u b l i s h e d data has r e s u l t e d in
a p h ase d i a g r a m f o r the F e - C s y s t e m which d i f f e r s
only s l i g h t l y f r o m o t h e r s r e c e n t l y published. It b r i n g s
into a g r e e m e n t the m e a s u r e d t h e r m o d y n a m i c p r o p e r t i e s of i r o n and the o b s e r v e d a c t i v i t i e s of the c o m p o nents in a - , ~ - and liquid s o l u t i o n s , and the f r e e e n e r g i e s of the c a r b i d e p h a s e s . P r o p e r t i e s of the a , 7,
5 and liquid so l u t i o n s a r e g i v e n in e q u a t i o n s , g r a p h s ,
and t a b l e s f r o m which the f o l l o w i n g f r e e e n e r g y , e n thalpy, and e n t r o p y data a r e d e r i v e d . In the e qua t i ons
YC is the a t o m r at i o n C / r i F e ; z C = YC / ( 1 - Y C); and
~C is the a c t i v i t y c o e f f i c i e n t a c / z C , the a c t i v i t y of
g r a p h i t e b ei n g taken as unity.
Th e c h a n g e in f r e e e n e r g y a c c o m p a n y i n g the s o l u tion of g r a p h i t e in ~,-Fe at i n f i n i t e dilution is obtained
f r o m Eq. [5] which is now u s e d in p r e f e r e n c e to the
a n a l o g o u s E q . [9] of Ref. 8:
C ( g r a p h i t e ) = C(in ~ - F e )
AG~

= 10,520-- 4 . 2 1 T

[19]

This is the d i f f e r e n c e b e t w e e n the two s t a n d a r d s t a t e s ,

g r a p h i t e and the h y p o t h e t i c a l s t a t e with z c = 1 and a l l
METALLURGICAL TRANSACTIONS

other properties those of the infinitely dilute solution.

The effect of concentration on the partial molar free
energy is
G ~ = G-~(7, i n f . d i l . ) + R T In z C + 1 7 , 6 6 0 y C

= G~e (y) - 8 8 3 0 y ~

+ R T In (1 - Y C )

1.21]
For the solution of graphite
gives
C(graphite)
AG~

i n l i q u i d i r o n E q . [7 ]

= C(in/-Fe)

= 5400 -- 3 . 9 8 T

[22]

and
G-C(/) = G ~ ( l , i n f . d i l . ) + R T In z C
+ (3.29T + 15,550)y C

[23]

F r o m t h e s e i t i s e v i d e n t t h a t t h e h e a t o f s o l u t i o n in
c a l o r i e s i s 5400 + 1 5 , 5 5 0 y c w h i l e t h e i n c r e a s e i n e n t r o p y i s 3.98 - 3 . 2 9 y c - R In z C 9 F o r t h e l i q u i d s o l u tion the partial molar free energy of iron is
GFe(/) = G~e(l)-(1.65T

+ 7770)y~

+ RT

in ( 1 - Y c )

[24]
In c~-5-Fe the free energy of solution of carbon
E q . [9] i n t h e r a n g e 500 ~ to 1 7 6 8 ~ i s :
C(graphite)
s176

by

= C(in a\Fe)

= 25,400-

ll.40T

[25]

The heat of'solution is 25,400 cal and the entropy inc r e a s e i s 1 1 . 4 0 - R In z C 9 I n 5 - F e t h e a c t i v i t y o f i r o n

is appreciably different from unity and here the partial free energy is
GFe(5) = G~e (5)-RT

In (1 - Y C )

[26]

The free energy of formation and other properties

of cementite (assumed to be Fe~C) in the c~-Fe range
u p to 1 0 0 0 ~ a r e g i v e n i n T a b l e V. I n t h e y - F e r a n g e ,
1000 ~ to 1 4 2 1 ~
the free energy is approximately
3 F e "Y+ C ( g r a p h i t e )

= Fe3C(O)

A G ~ = 2685 - 2 . 6 2 5 T

[27]

The free energy of formation of the x-carbide

i n F i g . 8 i s , i n t h e r a n g e 4 5 0 ~ to 6 5 0 ~
2.2 Fe(a) + C(graphite)
AG ~ = 4850-

shown

= Fe2.zC(x)

2.50T

[28]

Both carbides are metastable at all temperatures

with
r e s p e c t to g r a p h i t e a n d i t s s a t u r a t e d s o l u t i o n i n i r o n .
Below a temperature
e s t i m a t e d a s 230 ~ to 350~ t h e
x-carbide is more stable than cementite.
An estimate of the free energy of formation of c-

carbide precipitate is made from reported observations during aging. From its apparent solubility and
that of graphite in c~-Fe we derive the equation
2.4 Fe a + C(graphite)

= Fee.4C(s precipitate)

METALLURGICAL TRANSACTIONS

[29]

Other available data on the system

bilities are shown in tables.

including solu-

[20]

F r o m t h e s e e q u a t i o n s it i s e v i d e n t t h a t w h e n g r a p h i t e
dissolves in austenite the increase in entropy is 4.21
-R
In z C c a l p e r ~ . g - a t o m , a n d i t s h e a t o f s o l u t i o n
in calories is 10,520 + 17,660y C. For iron the partial
m o l a r f r e e e n e r g y b y E q . [6] i s :
GFe(austenite)

AG = 1 9 , 3 0 0 -- 6 . 1 3 T

ACKNOWLEDGMENTS
The author is indebted to Stuart Nelson

and Donald

T . H a w k i n s f o r a s s i s t a n c e in c o m p u t a t i o n a n d to R a l p h
H u l t g r e n a n d to a n a n o n y m o u s r e v i e w e r f o r h e l p f u l
comments on the manuscript.
This study was supported at Massachusetts
Institute of Technology by
the Army Research Office--Durham, and the American
Iron and Steel Institute, and at Berkeley by the Inorganic Materials Research Division of the Lawrence
R a d i a t i o n L a b o r a t o r y a n d t h e U . S. A t o m i c E n e r g y
Commission.

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METALLURGICAL TRANSACTIONS