A Thermodynamic Analysis of the

Fe-C and Fe-N Phase Diagrams

o

JOHN AGREN

T h e e x p e r i m e n t a l i n f o r m a t i o n on the F e - C and F e - N phase d i a g r a m s a r e e v a l u a t e d in

o r d e r to be able to r e c a l c u l a t e the phase d i a g r a m s in c l o s e a g r e e m e n t with the e x p e r i -
m e n t a l i n f o r m a t i o n a v a i l a b l e . A n a l y t i c a l e x p r e s s i o n s f o r the Gibbs e n e r g y of p u r e i r o n
in the b c c and liquid s t a t e s r e l a t i v e to the fcc st at e have b e e n obtained by m e a n s of p o w e r
s e r i e s e x p a n s i o n s . A s e t of p a r a m e t e r s d e s c r i b i n g the Gibbs e n e r g y of the individual
p h a s e s is p r e s e n t e d .

T H E c l a s s i c a l way to c o n s t r u c t a phase d i a g r a m is width of the ot + 7 t w o - p h a s e r e g i o n . The e v a l u a t i o n s

by connecting the e x p e r i m e n t a l points by hand. How- w i l l be s i m i l a r to H a r v i g ' s but C h i p m a n ' s c h o i c e of e x -
e v e r , the e q u i l i b r i u m p h a s e d i a g r a m of a s y s t e m may p e r i m e n t a l data f o r the n o n v a r i a n t s o l i d - l i q u i d pha s e
be r e g a r d e d as a m a n i f e s t a t i o n of the t h e r m o d y n a m i c e q u i l i b r i a w i l l be u s e d . An a n a l y s i s of the F e - N s y s -
p r o p e r t i e s of the s y s t e m . A much m o r e p o w e r f u l way t e m w i l l a l s o be p r e s e n t e d which follows c l o s e l y the
to c o n s t r u c t the d i a g r a m is thus to a n a l y z e the e x p e r i - r e c e n t a n a l y s i s of H i l l e r t and J a r l . 7 Th e 1968 t e m -
m e n t a l data in t h e r m o d y n a m i c t e r m s and, if p o s s i b l e , p e r a t u r e s c a l e w i l l be u sed .
to c o m b i n e the phase e q u i l i b r i u m i n f o r m a t i o n with
t h e r m o c h e m i c a l data. T h i s method has been applied to
GIBBS E N E R G Y O F PURE IRON
the F e - C s y s t e m many t i m e s . T h e w o r k by D a r k e n
and G u r r y 1 and by Benz and E l l i o t t 2 d e s e r v e m e n t i o n - Inden s has shown that the following t y p es of e x p r e s -
ing. M o r e r e c e n t l y , H a r v i g 3 made a d e t a i l e d e v a l u a t i o n si o n s can d e s c r i b e the m a g n e t i c c o n t r i b u t i o n to the
of the solid e q u i l i b r i a and C h i p m a n 4 c o n s i d e r e d al l the s p e c i f i c heat of a f e r r o m a g n e t i c m e t a l A with a r a t h e r
e q u i l i b r i a in the F e - C s y s t e m . H o w e v e r , the equations good a c c u r a c y :
g i v e n by C h i p m a n f o r the Gibbs e n e r g y functions of the
individual p h a s e s do not quite r e p r o d u c e the d i a g r a m c~ ~ = K~R In 11 -+- ~7.3 for r < 1 [1]
he p r e s e n t s . E x a m p l e s a r e g i v e n in T a b l e I. Th e p r e s -
ent w o r k was s t a r t e d in o r d e r to obtain a s e l f - c o n s i s t -
c 2 fl : K f i A R in 7~ + 1 for 7 > 1 [2]
ent d e s c r i p t i o n of the F e - C s y s t e m . 7z 1
Both H a r v i g and C h i p m a n b a s e d t h e i r a n a l y s e s on
t h e r m o d y n a m i c functions f o r p u r e i r o n t a b u l a t e d by w h e r e 7- = T / T c , T C being the C u r i e t e m p e r a t u r e , and
O r r and C h i p m a n . 5 Quite r e c e n t l y , H i l l e r t and J a r l 6 K~ and K~A a r e two c o n s t a n t s c h a r a c t e r i s t i c of the e l e -
p r o p o s e d the use of t r u n c a t e d p o w e r s e r i e s e x p a n s i o n s m e n t A in its f e r r o m a g n e t i c and p a r a m a g n e t i c s t a t e s
to obtain a n a l y t i c a l e x p r e s s i o n s for the m a g n e t i c c o n - which a r e h e r e d en o t ed by o~ and t3, r e s p e c t i v e l y . The
t r i b u t i o n to the Gibbs e n e r g y . H i l l e r t and J a r l a l s o Gibbs e n e r g y w i l l then be obtained by i n t e g r a t i n g E q s .
e v a l u a t e d an e x p r e s s i o n f o r the n o n m a g n e t i c c o n t r i b u -
tion to the Gibbs e n e r g y of f e r r i t e r e l a t i v e a u s t e n i t e in
p u r e i r o n . When t h e i r e x p r e s s i o n was a p p li e d to the
F e - C s y s t e m and c o m b i n e d with v a r i o u s c a r b o n a c t i v i t y Table I. Nonvariant Equilibria in the FeC System According to Various
Evaluations Using the 1968 Temperature Scale
data, it was found to p r e d i c t a t w o - p h a s e r e g i o n , a + y,
which is n a r r o w e r than the e x p e r i m e n t a l one by about WtPct Carbon in
Temperature,
10 p c t . Th e s a m e type of e x a m i n a t i o n was then made Equilibrium ~ Liquid Austenite Ferrite
of the F e - N s y s t e m and a s i m i l a r r e s u l t was obtained.
The e x p e r i m e n t a l i n f o r m a t i o n on the ~ + ~ t w o - p h a s e Metastable Eutectic
fiel d in t h e s e s y s t e m s s e e m s to be so w e l l e s t a b l i s h e d Chipman, reported 1148 4.30 2.11
Chipman, recalculated 1137 4.21 2.07
that it is j u s t i f i e d to a d j u s t the d e s c r i p t i o n of the Gibbs Present evaluation 1148 4.31 2.12
e n e r g y f o r p u r e i r o n in o r d e r to obtain b e t t e r a g r e e - Stable Eutectic
m e n t . It should be n o t i c e d that H i l l e r t and J a r l e v a l u - Chipman, reported 1154 4.26 2.08
ated t h e i r p a r a m e t e r s to g i v e ajgreement with the heat Chipman, recalculated 1143 4.17 2.24
of t r a n s f o r m a t i o n at the two a / 7 t r a n s i t i o n points in Present evaluation 1154 4.26 2.09
Peritectic
p u r e i r o n and that i n f o r m a t i o n is s u b j e c t to s o m e e x - Chipman, reported 1495 0.53 0.17 0.09
perimental uncertainty. Chipman, recalculated 1488 0.569 0.172 0.096
An a n a l y s i s of the F e - C s y s t e m w i l l now be p r e - Present evaluation 1495 0.517 0.167 0.090
s e n t e d which is b a s e d on the d e s c r i p t i o n of the m a g - Metastable Eutectoid
ne t i c c o n t r i b u t i o n to the Gibbs e n e r g y of b c c - i r o n , Chipman, reported 727 0.77 0.0218
Chipman, recalculated 729 - 0.742 0.0223
g i v e n by H i l l e r t and J a r l and on the e x p e r i m e n t a l Present evaluation 727 - 0.766 0.0210
Stable Eutectoid
Chipman, reported 738 - 0.68 0.0206
JOHN AGREN is with the Division of Physical Metallurgy, The Ctdpman, recalculated 737 - 0.689 0.0214
Royal Institute of Technology, S-100 44 Stockholm 70, Sweden. Present evaluation 739 - 0.676 0.0196
Manuscript submitted November 21, 1978.
ISSN 0360-2133/79/1211-1847500.75/0
METALLURGICAL TRANSACTIONS A 9 1979 AMERICANSOCIETY FOR METALS AND VOLUME 10A, DECEMBER 1979 1847
THE METALLURGICALSOCIETY OF AIME
[1] and [2] a c c o r d i n g to the t h e r m o d y n a m i c definition phase field in the F e - C s y s t e m . It was thus accepted
of the Gibbs e n e r g y : in the p r e s e n t e v a l u a t i o n . The r e m a i n i n g condition,
T T n e c e s s a r y in o r d e r to e v a l u a t e the p a r a m e t e r s , was a
l e a s t s q u a r e fit to the e n t h a l p i e s of t r a n s f o r m a t i o n
G = GO + f cpdT- T f (cp/T)dT.
r e p o r t e d by B r a u n and Kohlhaas, 9 910 J / m o l at 1185 K
To To
and - 8 5 0 J / m o l at 1667 K.
The following v a l u e s were obtained:
Since it is not p o s s i b l e to f o r m u l a t e the e n t r o p y p a r t
of the Gibbs e n e r g y in t e r m s of e l e m e n t a r y functions ~ 4 = 1462.4 (J/tool)
H i l l e r t and J a r l 6 a p p r o x i m a t e d E q s . [1] and [2] with ~B : - 8.282 (J/mol)
the f i r s t t h r e e t e r m s in the M a c L a u r i n s e r i e s e x p a n - - h a 1.15
= (J/mol)
sions : - h~/2 : -- 0.00064 (J/tool)
c ~ ~ = 2 K ~ R ( T 3 + rV3 + ~ 5 / 5 ) for r < 1 [3] The r e c a l c u l a t e d t r a n s f o r m a t i o n e n t h a l p i e s a r e 1011
J / m o l at 1185 K and - 8 2 5 J / m o l at 1667 K. The value
: 2K R( + + for r > 1. [4] at 1667 K is in s a t i s f a c t o r y a g r e e m e n t with the value
of 836 J/mol chosen by Orr and Chipman, and 824
F o r the c a s e of b e e - i r o n they thus obtained using T C J/mol extrapolated from data by Morris, Foerster,
= 1043 K: KFfle = 0.7504 KFe Schultz and Zellars, I~ and it is within the error limits
a = 1.073, yielding:
of the experimental data by Braun and Kohlhaas. The
~ = -6507.4[ ( T / 1 0 4 3 ) - ' / 1 0 + (T/1043)-~4/315 value at 1185 K seems somewhat too high and it is
outside the error limits of Braun and Kohlhaas. They
+ (T/1043)-24/1500] (J/tool) for T > 1043 K reported 910 + 20 J/tool. The value from Darken and
[5] Smith 11 which was accepted by Orr and Chipman is
900 J/mol. On the other hand, the value falls inside
and the error limits for the value reported by Anderson
and Hultgren, ~2 941 + 84 J/mol. Anyway, the high value
~ =-9177.4 + 9 . 7 1 9 T - 9304.9[(T/1043)4/6 was accepted for the present purpose.
Fe
The difference in Gibbs energy between the two crys-
+ (T/1043)~~ + (T/1043)~6/600] ( J / m o l ) talline p h a s e s of i r o n can now be c a l c u l a t e d at a l l t e m -
for T < 1043 K [6] p e r a t u r e s . The c a l c u l a t e d v a l u e s fall v e r y close to
those of O r r and C h i p m a n . In the t e m p e r a t u r e r a n g e
where o~rnB 500 to 1000 K the d i s c r e p a n c y is always l e s s than 30
~Fe and ~ Fe denote the m a g n e t i c c o n t r i b u -
tion to the Gibbs e n e r g y , above and below the C u r i e J / m o l and in the r a n g e 1000 to 1800 K it is always l e s s
t e m p e r a t u r e r e s p e c t i v e l y . The m a g n e t i c c o n t r i b u t i o n than 10 J / m o l . The a g r e e m e n t with the r e s u l t s f r o m
thus a p p r o a c h e s z e r o at high t e m p e r a t u r e s . Kaufman and N e s o r 13 is v e r y good in the m e d i u m t e m -
The n o n m a g n e t i c p a r t of the specific heat is often p e r a t u r e r a n g e (i.e. 1100 to 1700 K). At lower t e m p e r a -
found to v a r y l i n e a r l y with the t e m p e r a t u r e , provided t u r e s both the p r e s e n t e v a l u a t i o n and the one p r e s e n t e d
that the t e m p e r a t u r e is s u f f i c i e n t l y high above the by O r r and C h i p m a n differ c o n s i d e r a b l y f r o m the r e -
Debye t e m p e r a t u r e : sults of Kaufman and N e s o r . At T = 500 K the d i f f e r -
ent a u t h o r s give: ( J / t o o l and J / m o l K)
c=~ + flT
The following r e l a t i o n s then hold: OGbcc _ OGfcc OSbcc -- osfcc
Fe ve ' re Fe
G =A +BT-o~T In T - f i / 2 T 2 [7] O r r and Chipman 3639 8.24
H =d + aT + ~/2T 2 [8] Kaufman and N e s o r 3150 7.09
The p r e s e n t a n a l y s i s 3665 8.44
where A and B a r e i n t e g r a t i o n c o n s t a n t s .
The v a l u e s f r o m the p r e s e n t a n a l y s i s fall r a t h e r close
F o r the d i f f e r e n c e in Gibbs e n e r g y b e t w e e n the f e r -
to those of O r r and Chipman. Below this t e m p e r a t u r e
r i t i c (bcc) and the a u s t e n i t i c (fcc) s t a t e s we thus ob-
no v a l u e s a r e a v a i l a b l e f r o m O r r and C h i p m a n . F o r
tain:
the e n t r o p y d i f f e r e n c e K a u f m a n and N e s o r give at T
~'Fe -- o,~
o,,~bcc
~'Fefcc = h A + A B T - h a T In T
= 300 K, h~162 = 6.56 J / m o l , K w h e r e a s the p r e s e n t
e v a l u a t i o n gives 8.62 J / m o l K. The d i s c r e p a n c y in
- Afi/2T 2 + ~ [9] e n t r o p y is c l o s e l y connected to the d i s c r e p a n c i e s in
t r a n s f o r m a t i o n e n t h a l p i e s m e n t i o n e d above. It is p o s -
where the last t e r m is c a l c u l a t e d a c c o r d i n g to Eqs. [5] sible that a b e t t e r a g r e e m e n t with the e x p e r i m e n t a l
or [6]. The four a d j u s t a b l e p a r a m e t e r s will now be enthalpy of t r a n s f o r m a t i o n at 1667 K and 1185 K could
evaluated in the following way. The t r a n s f o r m a t i o n be obtained by using a d i f f e r e n t e x p r e s s i o n for the
t e m p e r a t u r e s taken f r o m O r r and C h i p m a n ~ and c o r - m a g n e t i c c o n t r i b u t i o n to the d i f f e r e n c e in specific
r e c t e d to the 1968 t e m p e r a t u r e s c a l e a r e 1185 and heat. In this c o n n e c t i o n it should be e m p h a s i z e d that
1667 K. The condition that the d i f f e r e n c e in Gibbs the p r e s e n t author has made no a t t e m p t to account for
e n e r g y b e t w e e n the two p h a s e s must v a n i s h at the the two d i f f e r e n t s p i n - s t a t e s in the fcc f o r m of i r o n .
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 s gives two e g u a t i o n s . The This s p e c i a l effect will yield a m o r e c o m p l i c a t e d t e m -
value at 1000 K of ~ - ~ = 338 J / m o l proposed p e r a t u r e d e p e n d e n c y for the specific heat of ~ - i r o n
by O r r and C h i p m a n has p r e v i o u s l y 3'4 been s u c c e s s - and was taken into account by K a u f m a n and B e r n s t e i n 14
fully applied to d e s c r i b e the width of the a + ~ two- who t r e a t e d it in t e r m s of a s o - c a l l e d Schottky a n o m a l y .

1848 VOLUME 10A,DECEMBER 1979 METALLURGICALTRANSACTIONSA

The d i f f e r e n c e is not v e r y l a r g e in the high t e m p e r a -
t u r e r e g i o n but grows t o w a r d s lower t e m p e r a t u r e s .
T h e r e f o r e the p a r a m e t e r s in the p r e s e n t r e p o r t m u s t
not be used at t e m p e r a t u r e s below 500 K.
The Gibbs e n e r g y of the liquid phase r e l a t i v e to a u s -
t e n i t e will be d e s c r i b e d by the s a m e type of e x p r e s s i o n
as the n o n m a g n e t i c Gibbs e n e r g y of f e r r i t e r e l a t i v e to
a u s t e n i t e . The p a r a m e t e r s were a d j u s t e d to r e p r o d u c e
the following data f r o m O r r and C h i p m a n S (adjusted to
the 1968 t e m p e r a t u r e s c a l e ) :
c#p - c~cc : 22.03 - 8.351" 10-3 T ( J / m o l ) [10a]
m e l t i n g t e m p e r a t u r e for bee = 1811 K
~ e - ~ Fe : 13,807 ( J / m o l ) at 1811 K. [10b]
The l a t t e r value is lower than the value of 14,400 J / m o l
r e p o r t e d by B r a u n and Kholhaasfl
We now obtain:
~ Fe -- ~ Fe = - 1 1 , 2 7 4 + 163.878 T ~ 22.03 T In T
+ 4.1755. 10-3 T 2 (J/reel) [11]
yielding the m e l t i n g t e m p e r a t u r e for m e t a s t a b l e a u s -
t e n i t e a s 1801 K.
made of H a r v i g ' s d e s c r i p t i o n of f e r r i t e . The follow-
ing p a r a m e t e r s fall v e r y close to his in the n e i g h b o r -
hood of the eutectoid t e m p e r a t u r e but yield the follow-
ing c a r b o n contents at the p e r i t e c t i c t e m p e r a t u r e of
1768 K, 0.090 and 0.167 wt pct, r e s p e c t i v e l y .
L Fe~
Cv : 0 [17]
~ - ~ C = 62,184 - 20.425 T (J/tool). [18]
The liquid phase will now be d e s c r i b e d with the s a m e
model as a u s t e n i t e , i . e . with a : c = 1. The p a r a m e t e r
v a l u e s for ~ -- ~ and r~ CFeL
v were a d j u s t e d in o r d e r
to r e p r o d u c e t h e following i n f o r m a t i o n . The stable e u -
t e c t i c t e m p e r a t u r e was taken to 1427 K, the c o m p o s i -
tion of the e u t e c t i c liquid was taken to 4.26 wt pct c a r -
bon and the p e r i t e c t i c t e m p e r a t u r e was taken to 1768 K
in a g r e e m e n t with the choices used by C h i p m a n in his
e v a l u a t i o n . ~ F u r t h e r m o r e , a value of 5.40 wt pct c a r -
bon was taken for the s o l u b i l i t y of g r a p h i t e at 1875 K
a c c o r d i n g to a n e a r l i e r study by C h i p m a n . 16 In c o m -
b i n a t i o n with the d e s c r i p t i o n of the solid p h a s e s , this
was enough to fix the p a r a m e t e r s to the following
v a l u e s supposing that they v a r y l i n e a r l y with t e m p e r -
ature.

~ ~ = 28,012 - 19.317 T [19]

THE F e - C - S Y S T E M
- -

Harvig d e s c r i b e d the Gibbs e n e r g y of f e r r i t e and LFeL

Cv = - 1 2 ; 2 3 3 - 17.669 T [20]
a u s t e n i t e with a model suggested by H i l l e r t and Staf-
f a n s s o n . 15 The F e - C phase d i a g r a m was c a l c u l a t e d by s t a n d a r d
methods f r o m the new set of p a r a m e t e r s and the r e s u l t
G C = ~ C + RT In [l y c yc ] - c2 Y C L~ [12a] is p r e s e n t e d in F i g s . 1 to 3. The p e r i t e c t i c and the e u -
tectic e q u i l i b r i a a c c o r d i n g to this new e v a l u a t i o n and
a c c o r d i n g to C h i p m a n ' s r e p o r t and as c a l c u l a t e d f r o m
GFe = ~ 1,
+ R T a c ln[1 - Y C ] + atYC )2Lye
Co [12b] his t h e r m o d y n a m i c d e s c r i p t i o n a r e c o m p a r e d in T a b l e I.
The table d e m o n s t r a t e s that the p r e s e n t e v a l u a t i o n is
F o r f e r r i t e a = 1 and c = 3. F o r a u s t e n i t e a = c = 1. capable of r e p r o d u c i n g the v a l u e s for all the t h r e e -
The c o n c e n t r a t i o n p a r a m e t e r YC is r e l a t e d to the phase e q u i l i b r i a chosen by C h i p m a n s a t i s f a c t o r i l y
o r d i n a r y mole f r a c t i o n x C by w h e r e a s his own e v a l u a t i o n shows a l e s s s a t i s f a c t o r y
a g r e e m e n t . A d e t a i l e d c o m p a r i s o n of the c a l c u l a t e d

YC =c
a xc
l -x c
[13] phase b o u n d a r i e s in F i g s . 1 to 3 with the e x p e r i m e n t a l
i n f o r m a t i o n a v a i l a b l e , also showed an e x c e l l e n t a g r e e -
m e n t . It was thus found that the e x p r e s s i o n s and p a -
F o r a u s t e n i t e Harvig gave the following p a r a m e t e r s r a m e t e r s p r o p o s e d in the p r e s e n t study a r e capable
( c o r r e c t e d to the 1968 t e m p e r a t u r e s c a l e ) : of r e p r o d u c i n g the F e - C phase d i a g r a m with s a t i s f a c -
tory a c c u r a c y .
LFe7
Cv = - 2 1 , 0 7 9 - 11.555 T (J/reel) [14] Shiflet, B r a d l e y and A a r o n s o n 17 have c a l c u l a t e d th e
f e r r i t e / a u s t e n i t e e q u i l i b r i u m in the t e m p e r a t u r e r a n g e
~ - ~ = 46,115 - 19.178 T (J/mol) [15] 200 to 912~ T h e i r a p p r o a c h is q u a s i c h e m i c a l and
b a s e d on a m o d e l developed by M c L e l l a n and Dunn. 18
~ - 3~ - ~ = 3 9 , 8 2 8 - 193.296 T T h e y also c o m p a r e d the e q u i l i b r i u m c o m p o s i t i o n s
p r e d i c t e d by d i f f e r e n t q u a s i c h e m i c a l models for i n t e r -
+ 22.3452 T I n T
s t i t i a l alloys (their F i g s . 3 and 4). F i g s . 4 and 5 show
(J/reel). [16] the s a m e e x t r a p o l a t i o n of the f e r r i t e and a u s t e n i t e
phase b o u n d a r i e s a c c o r d i n g to the p r e s e n t a n a l y s i s .
F o r c o n v e n i e n c e , f e r r i t e and a u s t e n i t e will now be d e - The a g r e e m e n t is s a t i s f a c t o r y above the eutectoid t e m -
noted by o~ and V, r e s p e c t i v e l y . H a r v i g was m a i n l y i n - p e r a t u r e but the r e s u l t of the v a r i o u s e x t r a p o l a t i o n s
t e r e s t e d in the m e d i u m and low r a n g e of t e m p e r a t u r e s differ m a r k e d l y at lower t e m p e r a t u r e s .
and did not pay p a r t i c u l a r attention to the high t e m - It is i n t e r e s t i n g to notice that some of the q u a s i c h e m -
p e r a t u r e i n f o r m a t i o n . The c a r b o n c o n t e n t s which can ical models p r e d i c t a r e t r o g r a d e b e h a v i o r at low t e m -
be r e c a l c u l a t e d for the ~ / y e q u i l i b r i u m at the p e r i - p e r a t u r e s in both the ~ / ~ + y and T/T + ~ b o u n d a r i e s
t e e t i e t e m p e r a t u r e s e e m to be too high, 0.15 and 0.23 w h e r e a s such a b e h a v i o r was found only for the ~ / ~ +
wt pet, r e s p e c t i v e l y , as c o m p a r e d to the e x p e r i m e n t a l b o u n d a r y by the p r e s e n t a n a l y s i s . The q u a s i c h e m i c a l
i n f o r m a t i o n that s e e m s to favor v a l u e s in the r a n g e s m o d e l s y i e l d r a t h e r c o m p l i c a t e d e x p r e s s i o n s for the
0.10 to 0.11 and 0.15 to 0.18. A r e v i s i o n was thus G i b b s e n e r g y and it may be concluded f r o m the p r e s e n t

METALLURGICALTRANSACTIONSA VOLUME 10A, DECEMBER 1979-1849

 1850 1908

1830 },8,,K'
l
1800 ],,,,K ' ' " ' t' ' ' //' ' '

1810 L 1700 ~ /
1801
1667.5 K
1790 1600
Z Z

> 1770 1500 ,.~6 1499 K

1~27 K - -
1750 i ~400 aog 1420.5K

1730 *-- 1300

LO
1710

1690

1670 1000 :. . . .

1650 800
0 0.1 0 . 2 0 . 3 o . q O.S 0 . 6 0 . 7 0 . 8 0 . 9 .0 0 0.8 1.6 2 . q 3.2 q.e q.8 5.6 6.q 7.2 8.0
HE I GHT-PERCENT C NEIGHF-PERCENT C
Fig. l -Peritectic part of calculated Fe-C phase diagram. Fig. 3-Calculated Fe-C phase diagram. The horizontal dashed lines
show the stable three phase equilibria L/~/graphite and 7/c~/graphite.
lqO0
1200 I I -+ I --- ,

1350
1120
1300
lOqO
1250
Z 960 F
z
.J 1200
LJJ 1185K }2 //// ~§ cem 880
W
i150
ILl

ii00
\\ ///7
w
800

728
c~
O-
IE: 1050
6qo
w
1000
0,765 1000 K 560
950 * cem
q80
900
01 ~ 1 '~' I I I 21" 0 I q00
0 .5 .0 1.5 2.5 I ' J , .112 I " -

NEI GHT-PERCENT C 0 .Oq .08 0 ~.16 0.20

Fig. 2-Eutectoid part of calculated Fe-C phase diagram. Solid and X-FRACTION C
dashed lines show the metastable and stable equilibria respectively. Fig. 4-Calculatedaustenite/~rritephaseboundaryin Fe~.

analysis that such models a r e not n e c e s s a r y in o r d e r accept the following p a r a m e t e r s f r o m Hillert and J a r l
to give a s a t i s f a c t o r y description of the F e - C s y s t e m . ( c o r r e c t e d to the 1968 t e m p e r a t u r e scale):
The p r e s e n t a n a l y s i s was based upon an e x p r e s s i o n
for the carbon activity in austenite taken f r o m the work LNv =0 [21]
of B a n - y a et al. 19 It uses the ideal configurational en-
t r o p y for the interstitial solution of c a r b o n in austenite. ~ - 1/2 o~gas
t, N2 = 21,378+ 139.858 T
The s u c c e s s of the p r e s e n t analysis lends f u r t h e r sup-
port for the use of the ideal configurattonal entropy. - 10.9077 T In T (J/tool) [22]

REVISION OF THE Fe-N SYSTEM LNvF : e-26,150

7 (J/tool). [23]

Hillert and Jarff have successfully applied the same Repeating the same procedure as described in Ref. 7
regular solution model to the Fe-N-system. However, for austenite and Fe4N(y') we now find the following
they based their evaluation on the Gibbs energy func- parameter values :
tion for pure iron tabulated by Orr and Chipman.~
Hence, it is necessary to adjust their parameters in O as
~ -1/2 G~2 = - 3 7 , 2 0 2 + 179.756 T
order to make them consistent with the new expres-
sion for the Gibbs energy of iron. For ferrite we can - 13.07 T I n T (J/mol) [24]

1850-VOLUME 10A, DECEMBER 1979 METALLURGICALTRANSACTIONSA

 1200 . . . : , : _' L - - 1200 i * i , I ,

1120 :16o ~ F

lOqO 1120

960 1080
Z
_:~ a,+ F
880 io,4o
L~
2~ O~
800 1000

720 '- 960

Lad LU
6q0 F ~- 920
~J

560 880

q80 8qO

800 r I ,
q00 l I I I I I I I I
0 .03 .06 .09 0.12 0.15
0 2 q 6 8 10 12 lq t6 18 20
WE I GHT-PERCENT N
X-FR~CTION C *10 -q Fig. 7 - C a l c u l a t e d
f e r r i t e / a u s t e n i t e phase boundary in Fe-N showing
Fig. 5-Calculatedfe~ite/austenitephasebounda~ in Fe~,showing the retrograde behavior of the a/c~+ 7 boundary.
there~ogradebehaviorofthe~/~+?bounda~.

1200 T h e new v a l u e of ~ - ~ is v e r y c l o s e to the v a l -

1160 [ u es c h o s e n in R e f s . 7 and 20 and it is within 13 pct of

the v a l u e of the t r i p l e point a / 7 / 9 a c c o r d i n g to Kaufman
and B e r n s t e i n . t4 T h e i r e v a l u a t i o n p r e d i c t s a m e t a s t a -
1120 ble t r a n s f o r m a t i o n 7 - E on cooling below a t e m p e r a -
t u r e of about 400 K, w h e r e a s the constant v a l u e c h o s e n
1080
Z in R e f s . 7 and 20 and in the p r e s e n t work, r e s u l t s in
lOqO
the p r e d i c t i o n that the ~ p h a s e should be m o r e stable
l.iJ than the 9 p h a s e at al l t e m p e r a t u r e s . H o w e v e r , it was
l.*J
i000 a r g u e d a l r e a d y in Ref. 7 that the c o n s t a n t v a l u e used
F )'+' 9 in the a n a l y s i s of the F e - N s y s t e m should only be used
F--
960 f o r that p u r p o s e and not be u s e d f o r an e x t r a p o l a t i o n
to p u r e i r o n . Th e p r e s e n t a u t h o r s h a r e s t h i s opinion
o- 920 and d o e s not q u e s t i o n the e x i s t e n c e of the m e t a s t a b l e
I--
880
, }'§ '/~ ~' t r a n s i t i o n point f o r 7 ~ 9
Th e F e - N p h ase d i a g r a m was c a l c u l a t e d and the r e -
su i t s a r e p r e s e n t e d in F i g s . 6 and 7. T h e r e a r e no s i g -
8qO
n i f i c a n t d i f f e r e n c e s in t h e s e d i a g r a m s c o m p a r e d to
t h o s e c a l c u l a t e d by H i l l e r t and J a r l . Th e t e m p e r a t u r e
800 I I I I I [I I 81 91
0 1 2 3 # S 6 7
and c o m p o s i t i o n at the v a r i o u s t h r e e - p h a s e e q u i l i b r i a
a r e s u m m a r i z e d in T a b l e II.
WE IGHT-PERCENT N
Fig. 6-Calculated Fe-N phase diagram.
M A G N E T I C ALLOYING EFFECTS

Of2"/'
Z e n e r 21 was the f i r s t one to r e a l i z e the i m p o r t a n c e
"r - 1/2 ~ = , 2 6 5 0 - 242.8 T
'JFe4N - 4 ~ Fe of the change in the C u r i e t e m p e r a t u r e by alloying e l e -
m e n t s . T h i s change will s t r o n g l y c o n t r i b u t e to the
+ 40.98 T In T (J/mol) [25] thermodynamic p r o p e r t i e s . Quantitative t r e a t m e n t s
have b e e n a t t e m p t e d by H i l l e r t , Wada and Wada 20 for
7 ' was thus t r e a t e d a s a s t o i c h i o m e t r i c c o m p on en t m e t a l l i c alloying e l e m e n t s in i r o n and by W a g n e r 23 f o r
Fe4N. In a l a t e r r e p o r t H e r t z m a n and J a r l ~~ s u g g e s t e d c a r b o n in c o b a l t . It is e v i d e n t that this e f f e c t should be
that a = 2 and c = 1 should be used in E q s . [12] and [13]
in the d e s c r i p t i o n of the hexagonal 9
T h e p a r a m e t e r s of the E-phase w e r e now e v a l u a t e d
Table II. Nonvariant Equilibria in the Fe-N System According to the
in the s a m e way a s in R e f . 20, y i e l d i n g :
Present Analysis Using the 1968 Temperature Scale
O s
GFe --~ = I469.3 (J/mot) [26] WtPet Carbonin
Equilibrium Temp, ~ a 7 e 7'
~ - ~ = - 4 4 6 0 - 11.98 T (J/tool) [27]
a/7/7' 592 0.] 02 2,407 - 5,898
LFee 7/e/7' 650 - 2.787 4.549 5.898
N V = - 12,496 (J/mol) [28]

METALLURGICAL TRANSACTIONS A VOLUME IOA, DECEMBER 1979-1851

c o n s i d e r e d in t h e s y s t e m s F e - C a n d F e - N b e f o r e a ACKNOWLEDGMENT
really satisfactory description can be obtained, This
This work is part of a project which is sponsored by
w a s n o t a t t e m p t e d in t h e p r e s e n t s t u d y s i n c e t h e e f -
the Swedish Board for Technical Development. The
fect of carbon and nitrogen on the Curie temperature
author wishes to thank Professor Mats Hillert for val-
of iron is not known,
uable advice and stimulating discussions.

RE FERENCES
SUMMARY 1. L. S. Darken and R. W. Gurry: The Physical Chemistry of Metals, McGraw-
Hill, New York, 1953.
In an attempt to obtain a consistent description of the 2. M. Benz and J. F. Elliott: Trans. TMS-AIME, 1961, vol. 221, pp. 323-31.
phase diagram and thermodynamic properties of the 3. H. Harvig:Yernkont. Ann., 1971, vol. 155, pp. 157-61.
Fe-C and Fe-N systems, a new expression for the dif- 4. J. Chipman: Met. Trans., 1972, vol. 3, pp. 55-64.
ference in Gibbs energy between bcc and fcc iron was 5. R. L. Orr and J. Chipman: Trans. TMS-AIME, 1967, vol. 239, pp. 630-33.
6. M. Hillert and M. Jarl: CALPHAD, 1978, vol. 2, pp. 227-38.
derived. The following result was obtained above and
7. M. HiUertand M. Jarl: Met. Trans. A, 1975, vol. 6A, pp. 553-59.
below the Curie temperature, respectively: 8. G. Inden: Project Meeting CALPHADV, June 1976, p. 111,4-1, Max Planck
Inst. Eisenforschung, GmbH Dfisseldorf, W. Germany, 1976.
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~ File - ~ ~e = 1462,4--8,282 T+ 1.15 T In T 10. J. P. Morris, E. F. Foerster, C. W. Schultz, and G. R. Zellars: U.S. Bur. Mines
Rept., lnvest. No. 6723, 1966.
1 T -4
- 6.4 9 10-4 T z - 6 5 0 7 , 4 [ ] - - 6 (1--6~) 11. L. S. Darken an d R. P. Smith: Ind. Eng. Chem., 1951, vol. 43, pp. 1815-20.
12. P. D. Andersson and R. Hultgren: Trans. TMS-AIME, 1962, vol. 224, pp.
1 T -14 1 T -24 842--45.
+~ (1---~) +~ (1---~-~) ] (J/mol) 13. L. Kaufman and H. Nesor: Z. Metallk., 1973, vol. 64, p. 249.
14. L. Kaufman and H. Bernstein: Computer Calculations of Phase Diagrams,
Academic Press, New York and London, 1970.
-~ Fe
=-7715 + 1.437 T+ 1,15 T In T 15. M Hillert andL.-I. Staffansson: Acta Chem. Seand., 1970, vol. 24, pp. 3618-
26.
16. J. Chipman, R. M. Alfred, L. W. Guernsey, and J. C. Fulton: Trans. ASM,
-- 6 . 4 " 10 -4 T 2 - 9 3 0 4 . 9 [ 6 (l__6_~)T4
1952,vol. 44, pp. 1215-30.
17. G. J. Shiflet, J. R. Bradley, and H. 1. Aaronson: Met. Trans. A, 1978, vol.
7A, pp. 999-1008.
+ ~1 (1-~43 ) lo + 6-'0"0
1 ( ~ )T 16 ] (J/mol). 18. R. B. McLellan and W. W. Dunn: J. Phys. Chem. Solids, 1969, vol. 30, pp.
2631-37.
19. S. Ban-ya, J. F. Elliott, and J. Chipman: Met. Trans., 1970, vol. 1, pp. 1313-
The analysis has yielded expressions for the Gibbs en- 20.
ergy of all the individual phases in the two systems and 20. S. Hertzman and M. Jarl: TRITA-MAC 0144, Materials Center, Royal Insti-
tute of Technology, S-100 44 Stockholm 70, Sweden, September 1978.
when the phase diagrams were recalculated, a satis- 21. C. Zener: Trans. AIME, 1955,vol. 203, p. 619.
factory agreement with experimental information was 22. M. Hillert, T. Wada, and H. Wada: J. Iron Steellnst., 1967, vol. 205, p. 539.
obtained. 23. C. Wagner: ActaMet., 1972, vol. 20, pp. 803-08.

1852-VOLUME 10A, DECEMBER 1979 METALLURGICAL TRANSACTIONSA