Activities in Liquid Fe-AI-O and Fe-Ti-O Alloys

R. J. FRUEHAN
The s o l u b i l i t y and a c t i v i t y of oxygen in F e - A 1 a n d F e - T i m e l t s a t 1600~ w e r e m e a s u r e d .
a c t i v i t y was m e a s u r e d e l e c t r o c h e m i c a l l y u s i n g the following g a l v a n i c c e i l s :

The

C r - C r 2 O s ( s ) ] ThO2(Y2Oa) i Fe-Al-_O(l), Al2Os(s)

C r - C r z O a ( s ) l ThOz(YaOs) ] Fe-Ti-O_(1 , s a t u r a t e d with oxide)
Cr-Cr2Oa(s) I ZrO2(CaO) I Fe-Ti-_O(l, s a t u r a t e d with oxide)
A l u m i n u m and t i t a n i u m d e c r e a s e the s o l u b i l i t y of oxygen in liquid i r o n to a m i n i m u m of 6 p p m
a t 0.09 wt o c t A1 and 40 p p m a t 0.9 wt p c t Ti, r e s p e c t i v e l y . The v a l u e of the i n t e r a c t i o n c o e f f i c i e n t s ~A1) and s TM a r e - 4 3 3 and - 2 2 2 , r e s p e c t i v e l y . The a c t i v i t y c o e f f i c i e n t of a l u m i n u m at
i n f i n i t e d i l u t i o n in l i q u i d i r o n is 0.021, while t h a t of t i t a n i u m is 0.038. The v a l u e of the a l u m i n u m e q u i l i b r i u m c o n s t a n t , the s o l u b i l i t y p r o d u c t at infinite dilution, i s 5.6 10 -*4 at 1600~
The
ThO2(Y2Oa) e l e c t r o l y t e e x h i b i t e d i n s i g n i f i c a n t e l e c t r o n i c c o n d u c t i v i t y a t 1600~ down to o x y g e n
p a r t i a l p r e s s u r e s of 10 -x6 a t m , which c o r r e s p o n d s to about 0.3 p p m O in u n a l l o y e d i r o n .

ALUMINUM

and t i t a n i u m a r e the s t r o n g e s t d e o x i d i z e r s c o m m o n l y u s e d in s t e e l m a k i n g . D e s p i t e the e x t e n s i v e w o r k done on the a l u m i n u m and t i t a n i u m d e o x i d a tion e q u i l i b r i a in l i q u i d i r o n , t h e r e s t i l l e x i s t s s o m e

u n c e r t a i n t y on the e q u i l i b r i u m d a t a .
The e a r l y w o r k of Wentrup a n d Hieber* i n d i c a t e d
t h a t the o x y g e n content in F e - T i - O a l l o y s a t 1600~ i s
a m i n i m u m of about 0.004 wt p c t a t 0.2 wt p c t Ti.
H a d l e y a n d D e r g e 2 d e t e r m i n e d the oxygen s o l u b i l i t y
and i d e n t i f i e d the e q u i l i b r i u m o x i d e p h a s e s . They
c o n c l u d e d that o x i d e p h a s e s w e r e liquid F e O - T i O z up
to 0.05 p c t Ti, TiO2 c o n t a i n i n g F e O f r o m 0.05 to 1 p c t
Ti, Ti2Os f r o m 1 to 5 p c t Ti, a n d TiO for h i g h e r t i t a n i um c o n t e n t s . They found t h a t the o x y g e n s o l u b i l i t y
r e a c h e d a m i n i m u m of b e t w e e n 0.002 and 0.004 p c t a t
about 0.5 p c t Ti at 1600~
Chino et al. a c a r r i e d out a
s i m i l a r i n v e s t i g a t i o n in which t h e y i d e n t i f i e d the o x i d e
p h a s e to b e TiaOs f o r a l l o y s c o n t a i n i n g f r o m 0.001 to
0.2 p c t Ti, TizO a f r o m 0.2 to 2.0 p c t , and TiO at h i g h e r
c o n c e n t r a t i o n s . They m a d e a few oxygen s o l u b i l i t y
m e a s u r e m e n t s which i n d i c a t e t h a t oxygen s o l u b i l i t y
m i n i m u m could be a s low a s 0.001 wt pct. T h e r e h a s
not b e e n a d i r e c t d e t e r m i n a t i o n of the a c t i v i t y of o x y gen o r t i t a n i u m in liquid F e - T i - O a l l o y s . Using the
r e s u l t s of H a d l e y and D e r g e , C h i p m a n 4 has m a d e a
rough e s t i m a t e of the a c t i v i t y c o e f f i c i e n t of t i t a n i u m
at i n f i n i t e dilution (7~ and of t h e i n t e r a c t i o n c o e f f i c i e n t e~TM ,
e~Ti)

d log fl~

= \ d ( w t p e t Ti)

"~

Cr-Cr~Oa(S)
Cr-Cr2Os(S)

[I]

]NFe_~ 1

w h e r e f o i s a c t i v i t y c o e f f i c i e n t of oxygen r e l a t i v e to
t h a t in p a r e i r o n . H o w e v e r , h i s v a l u e s a r e r o u g h e s t i m a t e s s i n c e t h e y r e q u i r e d e x t r a p o l a t i o n of d a t a with
s i g n i f i c a n t s c a t t e r and it w a s n e c e s s a r y to a s s u m e a
regular solution.
Gokcen and C h i p m a n 5 and Mc Lean and B e l l 8 m e a s u r e d the h y d r o g e n - w a t e r v a p o r m i x t u r e s in e q u i l i b r i u m with F e - A l - O m e l t s in a l u m i n a c r u c i b l e s at r e l a t i v e l y high t e m p e r a t u r e s (1695 ~ to 1866~
The a l u m i n u m a n d oxygen c o n t e n t s of l i q u i d i r o n in e q u i l i b r i u m with A12Oa w e r e m e a s u r e d b y d ' E n t r e m o n t e t al. 7
R. J. FRUEHAN is with the E. C. Bain Laboratory for Fundamental
Research, U. S. Steel Corp. Research Center, Monroeville, Pa.
Manuscript submitted April 27, 1970.
METALLURGICAL TRANSACTIONS

at 1740 ~ and 1910~ and b y S w i s h e r s a t 1580~

The
u n c e r t a i n t y s t i l l e x i s t i n g f o r the F e - A l - O e q u i l i b r i u m
i s e x e m p l i f i e d b y the wide r a n g e of e s t i m a t e s f o r the
i n t e r a c t i o n c o e f f i c i e n t e (A1) at 1600~
Gokcen and
C h i p m a n e s t i m a t e d e~A1) to b e - 12 c o m p a r e d to the
d ' E n t r e m o n t et a l . e s t i m a t e of - 1.0.
T h r e e of the m a j o r e x p e r i m e n t a l p r o b l e m s i n h e r e n t
in the t e c h n i q u e s u s e d in p r e v i o u s i n v e s t i g a t i o n s of the
F e - A 1 - O s y s t e m w e r e : i) a t t a i n m e n t of e q u i l i b r i u m
with the g a s p h a s e , ii) g a s s e p a r a t i o n due to t h e r m a l
d i f f u s i o n in the r e a c t i o n zone, and iii) the e r r o r s i n v o l v e d with the v a c u u m fusion technique f o r d e t e r m i n ing oxygen c o n t e n t s when the a l l o y c o n t a i n s s i g n i f i c a n t
a m o u n t s of a l u m i n u m . As p o i n t e d out b y d ' E n t r e m o n t
et a l . , v the v a c u u m fusion technique is not s u i t a b l e for
oxygen a n a l y s i s a t high a l u m i n u m c o n c e n t r a t i o n s , b e c a u s e of the a b s o r p t i o n of g a s b y the a l u m i n u m d i s t i l l e d f r o m the s a m p l e and the v a p o r i z a t i o n of A120
which c o n d e n s e s a t l o w e r t e m p e r a t u r e s .
T h e s e d i f f i c u l t i e s a r e e l i m i n a t e d b y m e a s u r i n g the
a c t i v i t y of o x y g e n in the m e l t e l e c t r o c h e m i c a l l y by the
use of a g a l v a n i c c e l l e m p l o y i n g a s o l i d o x i d e e l e c t r o tyte and a n a l y z i n g f o r oxygen b y the n e u t r o n a c t i v a t i o n
technique.
The g a l v a n i c c e l l s u s e d in the p r e s e n t i n v e s t i g a t i o n
can be r e p r e s e n t e d b y

Cr-Cr2Os(S)

ThO~(YeOs) I F e - A 1 - O ( / ) , A12Oa(s)
[I]
ThOe(Y2Os) L F e - T i - ~ ( / , s a t u r a t e d
with o x i d e )
[II]
ZrO2(CaO) ] F e - T i - O ( l , s a t u r a t e d
with o x i d e )
[III]

The r e l a t i o n s h i p b e t w e e n the a c t i v i t y of oxygen (ao) ,

which is equal to w e i g h t p e r c e n t in p u r e i r o n , and the
e l e c t r o m o t i v e f o r c e (E in mv) has b e e n d e r i v e d p r e v i o u s l y a and i s g i v e n b y
log ao = 4.62 -

13,580 - 10.03E
T

[2]

F o r a l l of the F e - A 1 a l l o y s i n v e s t i g a t e d , A120 a was

the e q u i l i b r i u m o x i d e p h a s e , i . e . a b o v e the a l u m i n u m
c o n c e n t r a t i o n f o r which h e r c y n i t e ( F e O . AltOs) is the
s t a b l e oxide p h a s e . *~ T h e r e f o r e , the o v e r - a l l c e l l r e a c t i o n can be r e p r e s e n t e d b y
~Cr2Os(s) + A1 - - Cr(s) + ~Alz~:)a(s)

[3]

VOLUME 1,DECEMBER 1970-3403

The r e l a t i o n s h i p b e t w e e n the a c t i v i t y of AI(aA1 ) and E

is given b y
nF

log aA1 - 2.303RT (Eo - E )

[4]

w h e r e n (= 3) is the n u m b e r of e q u i v a l e n t s p e r m o l e , F
is the F a r a d a y c o n s t a n t , and Eo is the e l e c t r o m o t i v e
f o r c e a c r o s s the e l e c t r o l y t e f o r a p u r e A1-Ai203 m e l t .
Since the value of E o could n o t b e d e t e r m i n e d e x p e r i m e n t a l l y , b e c a u s e ThO2(YaOa) exhibits s i g n i f i c a n t e l e c t r o n i c c o n d u c t i v i t y at the p a r t i a l p r e s s u r e s of oxygen
in e q u i l i b r i u m with Al20 a and p u r e a l u m i n u m , it was
c a l c u l a t e d f r o m the known f r e e e n e r g i e s of f o r m a t i o n
of Cr~Oa and Al2Oa. 11 The v a l u e of Eo at 1600~ was
c a l c u l a t e d to be - 732 mv.
F o r F e - T i - O (oxide s a t u r a t e d ) alloys containing
o v e r 5 wt pct Ti, it is g e n e r a l l y a g r e e d that 720 is the
e q u i l i b r i u m oxide phase so t h a t the o v e r - a l l cell r e a c t i o n for these alloys can be r e p r e s e n t e d by
Cr2Oa(s) + 72 ~

~ C r + 720

[5]

T h e r e f o r e , for alloys c o n t a i n i n g over 5 wt pct Ti the

a c t i v i t y of t i t a n i u m can be c a l c u l a t e d f r o m the e l e c t r o motive force,
nF
( E ~ - E)
log a T i - 2.303RT

[6]

w h e r e n = 2 and E~ is the c a l c u l a t e d e l e c t r o m o t i v e
f o r c e of the cell for the T i ( s ) - T i O ( s ) s y s t e m ( - 6 7 4
my) u s i n g the f r e e e n e r g y v a l u e s compiled by E l l i o t t
e t a l . It

In c a l c u l a t i n g the a c t i v i t i e s of a l u m i n u m and t i t a n i um in liquid i r o n , the effect of the t h i r d component,

oxygen, can be n e g l e c t e d s i n c e it is p r e s e n t in s m a l l
concentrations.
In o r d e r for Eqs. [2], [4], and [6] to be valid, the
e l e c t r o l y t e s m u s t exhibit i n s i g n i f i c a n t e l e c t r o n i c c o n d u c t i v i t y u n d e r the conditions of t h e i r use. ZrO~(CaO)
and ThOa(Y2Oa) have p r e v i o u s l y b e e n d e m o n s t r a t e d to
exhibit i n s i g n i f i c a n t e l e c t r o n i c conductivity at 1600~
at oxygen p r e s s u r e s as low as 3 10 -~3 a t m 9 and at
l e a s t 2 10-~6 atm, x2 r e s p e c t i v e l y .
EXPERIMENTAL
T h r e e types of g a l v a n i c c e l l c o n s t r u c t i o n were u s e d
in i n v e s t i g a t i n g the F e - A 1 - O s y s t e m . One c o n s i s t e d
of a ThO, (7 wt pct Y2Os) tube, 2 cm OD by 1 c m ID,
c l o s e d a t one end. The g e n e r a l c o n s t r u c t i o n of the
o t h e r two types has been d e s c r i b e d in d e t a i l e l s e w h e r e , g B r i e f l y , a ThOu (7 wt p c t Y203) p e l l e t , 4 m m
d i a m b y 4 m m high, was s e a l e d i n one end of a s i l i c a
tube o r c e m e n t e d in one end of an a l u m i n a tube with
h i g h - p u r i t y a l u m i n a c e m e n t . When a s i l i c a tube was
used, the tube was coated with a thin l a y e r of a l u m i n a
in o r d e r to p r o t e c t the s i l i c a which would o t h e r w i s e
be r e d u c e d in the m e l t . F o r a l l t h r e e types of c e l l s ,
the t u b e s were packed with a powder m i x t u r e of
Cr-Cr2Os, which acted as the r e f e r e n c e e l e c t r o d e .
Contact with the C r - C r 2 0 s e l e c t r o d e was made with
a p l a t i n u m w i r e . As d i s c u s s e d p r e v i o u s l y , " the p l a t i n u m w i r e did not r e a c t s i g n i f i c a n t l y with the C r - C r 2 0 3
e l e c t r o d e . Contact with the m e l t was made with a
c o m m e r c i a l l y available molybdenum cermet containing 80 pct Mo and 20 pct AIaOa. Its c o n s t r u c t i o n has
b e e n d e s c r i b e d p r e v i o u s l y f l When using the m o l y b d e 3404-VOLUME 1,DECEMBER 1970

n u m c e r m e t , as c o n s t r u c t e d , t h e r e is no need for a
t h e r m o e l e c t r o m o t i v e force c o r r e c t i o n a n d the c e r m e t
does not d i s s o l v e s i g n i f i c a n t l y in the m e l t .
The c e l l s used in studying the F e - T i - O s y s t e m were
e s s e n t i a l l y the s a m e in that a ZrO2(CaO) o r ThO2(Y2Os)
d i s k was s e a l e d into a s i l i c a tube. The o n l y d i f f e r e n c e
with the c e l l s u s e d was that contact with both the
Cr-Cr~Os e l e c t r o d e and the m e l t was m a d e with a
m o l y b d e n u m w i r e . As d i s c u s s e d p r e v i o u s l y , a m o l y b d e n u m contact is s a t i s f a c t o r y in s t u d i e s of this typefl
The i n i t i a l i r o n used was p r e p a r e d b y v a c u u m c a r b o n deoxidizing e l e c t r o l y t i c i r o n ; the m a i n i m p u r i ties being
Si--0.004 wt p c t
C r - - 0 . 0 0 5 wt p c t
Zr--0.001 wt p c t

Mn--0.004 wt pct
0 - - 0 . 0 0 4 wt pct
C--0.002 wt pct

The F e - A l m e l t s were contained in h i g h - p u r i t y r e c r y s t a l l i z e d a l u m i n a c r u c i b l e s while the F e - T i m e l t s

were contained in e i t h e r ThO~ or ZrO2 c r u c i b l e s . ThO2
and ZrO2 c r u c i b l e s a r e s u i t a b l e c o n t a i n e r s for F e - T i O (oxide s a t u r a t e d ) m e l t s s i n c e both ThO2 and ZrOa a r e
m o r e s t a b l e than the oxides of t i t a n i u m , 11 so that t h e r e
is no s i g n i f i c a n t r e d u c t i o n of c r u c i b l e m a t e r i a l . Also,
ThOu and ZrO2 do not f o r m a liquid oxide s o l u t i o n with
the oxides of t i t a n i u m 13 at 1600~
Hadley and Derge 2
r e p o r t e d no n o t i c e a b l e d i f f e r e n c e in the c o n c e n t r a t i o n
of oxygen at s a t u r a t i o n in F e - T i a l l o y s when the m e l t s
were held in TiO~ MgO, AlcOa, or ZrO2 c r u c i b l e s . The
e x p e r i m e n t s w e r e c a r r i e d out in a v e r t i c a l Mo w i r e wound r e s i s t a n c e f u r n a c e which was c o n t i n u o u s l y
flushed with p u r i f i e d argon. The t e m p e r a t u r e was
m e a s u r e d with a P t - P t / 1 0 pct Rh t h e r m o c o u p l e .
The e x p e r i m e n t a l p r o c e d u r e was e s s e n t i a l l y the
s a m e as that d e s c r i b e d p r e v i o u s l y , t4 When the t e m p e r a t u r e r e a c h e d 1600~ d e s i r e d a m o u n t of a l u m i n u m
o r t i t a n i u m was added to the m e l t ; a f t e r waiting a s u f f i c i e n t t i m e to e n s u r e e q u i l i b r i u m , about t h i r t y m i n utes, a cell was l o w e r e d into the t n e l t a n d an emf
r e a d i n g taken. Stable r e v e r s i b l e r e a d i n g s were o b t a i n e d for as long as t h i r t y m i n u t e s b e f o r e r e m o v i n g
the c e l l s f r o m the m e l t . In m o s t c a s e s two c e l l s were
used and they a g r e e d within 2 my. T h e r e was no s i g n i f i c a n t d i f f e r e n c e in the stable emf r e a d i n g when
d i f f e r e n t types of c e l l s w e r e used in the s a m e melt.
In the i n v e s t i g a t i o n of Fe-A1-O, the m e l t s were in
e q u i l i b r i u m with the A120s c r u c i b l e . In the case of
F e - T i - O , the e q u i l i b r i u m oxide p h a s e was f o r m e d
b y the r e a c t i o n of the added t i t a n i u m with the oxygen
in the m e l t . The p r e s e n c e of an oxide p h a s e was c o n f i r m e d v i s u a l l y and when n e c e s s a r y oxygen was added
in the f o r m of i r o n oxide.
After s a t i s f a c t o r y emf r e a d i n g s w e r e obtained,
s a m p l e s of the m e l t were taken by s u c t i o n into a
s i l i c a tube, 5 m m ID, and quenched in ice w a t e r .
C a r e was t a k e n in the handling and the p r e p a r a t i o n
of the s a m p l e s for a n a l y s i s . Only the m i d d l e of the
s a m p l e was u s e d for a n a l y s i s ; all of the s a m p l e s
used were sound and upon close e x a m i n a t i o n showed
no e n t r a p p e d oxide i n c l u s i o n s . The s a m p l e s were
c l e a n e d by m a c h i n i n g off the s u r f a c e , u s u a l l y r e d u c ing the d i a m e t e r to about 4 m m . D u r i n g m a c h i n i n g
the s u r f a c e of the s a m p l e was kept cool with acetone
in o r d e r to avoid s u r f a c e oxidation. The s a m p l e s were
a n a l y z e d for oxygen by n e u t r o n a c t i v a t i o n with t h r e e
o r four d e t e r m i n a t i o n s made on each s a m p l e . The
METALLURGICALTRANSACTIONS

s a m p l e s were a n a l y z e d for a l u m i n u m or t i t a n i u m
c h e m i c a l l y in the usual m a n n e r .

RESULTS AND DISCUSSION

Fe-A1-O

- 1.0

The s o l u b i l i t y of oxygen in F e - A l m e l t s in e q u i l i b r i u m with AlaOs at 1600~ is p r e s e n t e d in Table I and

p l o t t e d in Fig. 1. The s o l u b i l i t y d e c r e a s e s with i n c r e a s i n g a l u m i n u m content to a m i n i m u m of about 6
p p m at 0.09 pct Al and then i n c r e a s e s rapidly. M i n i m u m p o i n t s in oxide s o l u b i l i t i e s have b e e n found for
s e v e r a l s i m i l a r s y s t e m s , F e - C r - O !~'~S and F e - V - O . ~6
This b e h a v i o r is due to the l o w e r i n g of oxygen a c t i v i t y
c o e f f i c i e n t with i n c r e a s i n g a l u m i n u m content. T h e s e
r e s u l t s a r e in r e a s o n a b l e a g r e e m e n t with the p r e v i o u s
r e s u l t s a t h i g h e r t e m p e r a t u r e s of McLean and Bell, 6
d ' E n t r e m o n t e t a l . , 7 and Gokcen and Chipman. 5 The
only p r e v i o u s work done n e a r 1600~ was that of
Swisher. a The r e s u l t s of S w i s h e r a p p e a r to be i n c o n s i s t e n t with o t h e r data. At r e l a t i v e l y high a l u m i n u m
c o n t e n t s , his m e a s u r e d oxygen c o n t e n t s a r e lower than
one would expect for the following r e a s o n s . F o r a l l o y s
c o n t a i n i n g up to 10 wt pet A1, he r e p o r t s l e s s than 10
ppm of oxygen. Even u s i n g a v a l u e as s m a l l as - 0.7
for e (AI), and the e q u i l i b r i u m c o n s t a n t If, c o n c e n t r a tions of oxygen o v e r 300 p p m would be expected at 5
wt p c t A1. If eo(Al) were m o r e n e g a t i v e , even h i g h e r
oxygen c o n c e n t r a t i o n s would be expected. Also at

Table I. The Solubility and Activity of Oxygen in Fe-AI Alloys at 1600~

Aluminum,
wt pct

Oxygen
ppm

E, mv

-log.f~

10
7
8
5
7
8
14
31
48

-102
-171
-187
-212
-262
-310
-351

0.13
-0.44
0.34
0.68
1.22
1.89
2.21

0.02
0.06
0.07
0.09
0.10
0.15
0.35
0.85
1.40

*Relativeto unalloyedironwherefo = 1.0. CellI usedfor all measurements.

Al,wt.%
0.05
0.2

0.01
1

0.5
I

2.0
I

d'ENTREMONT et01 (1910~

-2.0

-200

\.~

100
"\

_o

50

~:

S
-5.0

10 o

SWISHER (1580~
-2
-4.0

-2.0

-I.0
10g (al %)

Fig. 1--The solubility of oxygen in Fe-A1 melts in equilibrium

with A1203 at 1600~
METALLURGICALTRANSACTIONS

Fig. 2--Log f0 vs aluminum concentrations

in Fe-A1 melts at
1600~

-2.0 -

0.5

1.0

1.5

A1, wt.%

h i g h e r Al c o n c e n t r a t i o n the oxygen c o n t e n t would be

greater.
The e r r o r in S w i s h e r ' s r e s u l t s is b e l i e v e d to a r i s e
f r o m his m e t h o d of oxygen a n a l y s i s . As p o i n t e d out
p r e v i o u s l y , the v a c u u m fusion technique is s u b j e c t to
s i g n i f i c a n t e r r o r at high a l u m i n u m c o n t e n t s , due to
the a b s o r p t i o n of gas by the a l u m i n u m d i s t i l l e d f r o m
the s a m p l e and the v a p o r i z a t i o n of Al20. This would
a c c o u n t for the low oxygen contents at high a l u m i n u m
concentrations 9
The a c t i v i t y coefficient of oxygen (fo) ( r e l a t i v e to
unalloyed i r o n ) is shown as a function of a l u m i n u m
c o n c e n t r a t i o n in Fig. 2. The a c t i v i t y of oxygen was
d e t e r m i n e d d i r e c t l y f r o m the e l e c t r o m o t i v e m e a s u r e m e n t . The v a l u e of log fo is a p p r o x i m a t e l y a l i n e a r
function of c o m p o s i t i o n up to 0.3 wi pct Al. However,
at high a l u m i n u m c o n c e n t r a t i o n s log )Co is no longer a
l i n e a r function. This is s i m i l a r to what was found for
F e - C r - O , 14 F e - V - O , le and F e - T i - O to be d i s c u s s e d
l a t e r 9 The slope up to 0.3 wi pct Al, e(oAI) , is - 3.90.
As shown by Lupis and Elliott, 17 the v a l u e of e~AI) can
be d e t e r m i n e d f r o m e(oAI).

: (

in
d N A1

[71
NFe~ 1

e~A1) = 230 MA1 e (A1) + M o -- M A I

MF e o
MF e

[8]

where M is the a t o m i c weight. The v a l u e of EgAI) is

-433.
S i m i l a r e x p r e s s i o n s were used for d e t e r m i n i n g
e~l) and e ~ ). T h e s e two q u a n t i t i e s a r e - 6.59 and - 433,
respectively.
The i n t e r a c t i o n coefficient e (A1) at 1600~ d e t e r m i n e d in the p r e s e n t work ( - 3 . 9 0 ) is to be c o m p a r e d
with the p r e v i o u s l y d e t e r m i n e d v a l u e s of Gokcen and
Chipman s ( - 12), M c L e a n and Bell e ( - 4.6), and
d ' E n t r e m o n t e t a l . ? ( - 1.0). All the v a l u e s , except the
p r e s e n t one, w e r e e x t r a p o l a t e d f r o m h i g h e r t e m p e r a tures.
The e a r l y work of Gokcen and C h i p m a n was l i m i t e d
to a l u m i n u m c o n c e n t r a t i o n s l e s s than 0.025 wt pct.
T h e i r value of e (A1) was b a s e d on the d e p e n d e n c e of
(H20/Hz)[0% ] on a l u m i n u m c o n c e n t r a t i o n . T h e i r value
is, t h e r e f o r e , only a rough e s t i m a t e , c o n s i d e r i n g the
s m a l l a l u m i n u m c o n c e n t r a t i o n r a n g e and the d i f f i c u l ties in a n a l y z i n g for such q u a n t i t i e s of a l u m i n u m .
d ' E n t r e m o n t e t a l . b a s e d t h e i r v a l u e s of eo(At) on the
dependence of the s o l u b i l i t y product, K' = ( p c t Al)~
9 (pct O) s, on a l u m i n u m c o n c e n t r a t i o n and the a v a i l a b l e
VOLUME 1,DECEMBER 1970-3405

d a t a on the a c t i v i t y of a l u m i n u m in F e - A 1 a l l o y s . Is In
t h e i r c a l c u l a t i o n s t h e y a s s u m e d log f0 to be a l i n e a r
function of wt p c t A1 o v e r t h e i r e n t i r e c o m p o s i t i o n
r a n g e . T h e r e f o r e , the m a j o r r e a s o n for the d i s c r e p a n c y b e t w e e n t h e i r work and the p r e s e n t w o r k is t h a t
log f o i s not a l i n e a r function of wt p c t A1 o v e r 0.3 wt
p e t . Since m o r e than half of the d ' E n t r e m o n t et al.
d a t a w e r e taken a t a l u m i n u m c o n c e n t r a t i o n s above
0.5 wt p c t , t h e i r v a l u e w i l l be c o n s i d e r a b l y l o w e r than
the i n i t i a l value w h e r e e(oA1) is r e l a t i v e l y c o n s t a n t . It
is n o t e w o r t h y that the v a l u e of l o g f 0 / p c t A1 d e t e r m i n e r
in the p r e s e n t study a t the h i g h e s t a l u m i n u m c o n c e n t r a t i o n i n v e s t i g a t e d (1.4 p c t ) is about - 1.5 which is in
f a i r a g r e e m e n t with d ' E n t r e m o n t et al. H o w e v e r , in
the c o m p o s i t i o n r a n g e of m a j o r i n t e r e s t (< 0.3 p c t A1)
e~AI) i s c o n s t a n t and equal to - 3 . 9 0 . This d i s c r e p a n c y
p o i n t s out the i m p o r t a n t f a c t t h a t the v a l u e of log f i i s
a l i n e a r function of j wt p c t o n l y in the l i m i t i n g c a s e ,
a s j wt p c t a p p r o a c h e s z e r o . T h e r e f o r e , any c a l c u l a tion d e t e r m i n i n g ez(J) o r using e~J) m u s t be done in the
c o m p o s i t i o n r a n g e w h e r e i t s v a l u e is r e l a t i v e l y c o n stant.
The r e s u l t s of M c L e a n and B e l l e a r e in e x c e l l e n t
a g r e e m e n t with the p r e s e n t v a l u e c o n s i d e r i n g the e x t r a p o l a t i o n of M c L e a n and B e l l ' s d a t a f r o m 1723~
They u s e d only two d a t a p o i n t s , one at 1823 ~ and the
o t h e r a t 1723~ in d e t e r m i n i n g the t e m p e r a t u r e d e p e n d e n c e of e(0Al) . In Fig. 5, e ~ d) is p l o t t e d vs l I T
using both s e t s of d a t a i n d i c a t i n g that the r e s u l t s a r e
c o n s i s t e n t with t h o s e of M c L e a n and Bell. The t e r n -

Table

I I. The Activity of Aluminum in Fe-AI Alloys at 1600~

(Relative to Liquid Aluminum)

Electromotive
NAI
0.0004
0.0015
0.0018
0.0032
0.0072
0.0173
0.0293

Force, mv

aAl X 103

-log 7A I

0.083
0.294
0.398
0.645
1.550
3.630
8.310

1.68
1.71
1.66
1.69
1.67
1.68
1,54

-102
-171
-187
-212
-262
-310
-351

Cell I used for all measurements.

Table III. Thermodynamic Quantities for Fe-AI-O and Fe-Ti-O Alloys at

Parameter
e~X)
e(Ox)
e(xO)
e(XO)
gtFe.X
ax_ o
e(xx)
e(xx)

7X

Fe-A1-O
-3,90
-433
-6.59
-433
--2.21
-190
-0.091
-10
0.021

1600~
Fe-Ti-O
-1.12

-222
-3.75
-222
-0.6

1.2 "

1.4

.I.-.~--'l'"

WILDER& E L L I j O T T

~ -1.6
-I.8 b~"~
t.0

0.98

096

0.94

092

Nz
Fe
F i g . 3 - - L o g YAI in F e - A 1 a l l o y s at 1600~

p e r a t u r e d e p e n d e n c e of e(oAI) for the t e m p e r a t u r e r a n g e

1600 ~ to 1823~ is given by
e~A1) =

20,600
T

+ 7.15

[9]

The h e a t - l i k e t e r m kJj) d e t e r m i n e d f r o m the t e m p e r a t u r e d e p e n d e n c e of e !j) h a s been d e f i n e d b y Lupis and

E l l i o t t z9 a s
de~j)
j) -- 2 . 3 n d

[10]

1/T

l, (0)
The v a l u e s of ho(AI) d e t e r m i n e d f r o m Eq. [9] and r~Al
a r e p r e s e n t e d in T a b l e III.
The a c t i v i t y of a l u m i n u m in F e - A 1 m e l t s d e t e r m i n e d
f r o m m e a s u r e d e l e c t r o m o t i v e f o r c e s i s p r e s e n t e d in
T a b l e II. The v a l u e of Iog 7A1 is not a l i n e a r function
of NAI but of N ~ e a s d e m o n s t r a t e d b y B e l t o n and
F r u e h a n f l ~ In F i g . 3, log TA1 is p l o t t e d v s N ~ e . The
v a l u e of t~FeA1 , d e f i n e d by D a r k e n 2t a s

log YA1 = O t F e A 1 N F e + I

[11]

could not be d e t e r m i n e d b e c a u s e of the s m a l l c o m p o s i tion r a n g e i n v e s t i g a t e d . The value of CrFeA1 = --2.21

d e t e r m i n e d f r o m the w o r k of Belton and F r u e h a n is
used in d r a w i n g the line in Fig. 3 for the p r e s e n t work.
The v a l u e s e s t i m a t e d b y W i l d e r and E l l i o t t za a r e a l s o
given in Fig. 3 f o r c o m p a r i s o n .
F o r the s m a l l a l u m i n u m c o n c e n t r a t i o n involved in
a l u m i n u m d e o x i d a t i o n of s t e e l , the i n t e r a c t i o n c o e f f i c i e n t t e r m i n o l o g y m a y be u s e d a s an a p p r o x i m a t i o n
even though log YA1 is not a s t r i c t l y l i n e a r function of
NA1. The v a l u e s of e(A1
M) and c ~ ) c a l c u l a t e d f r o m the
value of CgFeA1 d e t e r m i n e d by Belton and F r u e h a n a r e
- 0.091 and - 10, r e s p e c t i v e l y . It s h o u l d be e m p h a s i z e d t h a t t h e s e v a l u e s a r e v a l i d only f o r s m a l l c o n c e n t r a t i o n s of a l u m i n u m s i n c e the F e - A 1 s y s t e m is
b e s t r e p r e s e n t e d by the q u a d r a t i c f o r m a l i s m . D a r k e n 22
has also defined quadratic formalism constants for
t e r n a r y a l l o y s . The c o n s t a n t aAl O d e f i n e d b y Eq. [12],
which is v a l i d at infinite dilution, is e q u a l to - 190

-96
-0.014
-2.70
0.038

h(ox)

-94 kcal/mole

h(xO)

- 159 kcal/mole

3 4 0 6 - V O L U M E I , D E C E M B E R 1970

s (A1) = 2.303 (aAi O -- OtFeO -- aFeA1 )

[12]

The v a l u e s of the v a r i o u s p a r a m e t e r s f o r F e - A 1 - O
s y s t e m a t 1600~ a r e s u m m a r i z e d in T a b l e III.
The a c t i v i t y of a l u m i n u m in Fe-A1 a l l o y s d e t e r m i n e d
f r o m the e l e c t r o m o t i v e f o r c e s is in good a g r e e m e n t
with the p r e v i o u s m a s s s p e c t r o m e t r i c w o r k of Belton
F r u e h a n . The s m a l l d i f f e r e n c e in the v a l u e s of log yoA1
METALLURGICAL TRANSACTIONS

= - 1 . 6 8 in t h e p r e s e n t w o r k c o m p a r e d to - 1.62 d e t e r mined previously may be attributed to the uncertaint i e s i n t h e f r e e e n e r g i e s of f o r m a t i o n f o r C r a O 3 a n d

AlaO a. T h e d i f f e r e n c e of 0 . 0 6 i n l o g ~2AI c o r r e s p o n d s
t o a b o u t 500 c a l u n c e r t a i n t y f o r t h e o v e r - a l l c e l l R e a c t i o n [3]. T h i s i s w e l l w i t h i n t h e u n c e r t a i n t i e s i n f r e e
e n e r g i e s of f o r m a t i o n of AlaO s a n d C r a O s.
T h e e q u i l i b r i u m c o n s t a n t , K , a t 1600~ f o r t h e a l u minum deoxidation reaction in liquid iron determined
f r o m t h e d a t a i n T a b l e I i s 5 . 6 10 -t4
2A1 (1 w t p e t ) + 3 0 (1 wt p c t ) = AlaOs(s )
3

[13]

K = aoaA1
T h i s v a l u e i s in r e a s o n a b l e a g r e e m e n t w i t h p r e v i o u s
d e t e r m i n a t i o n s a s d e m o n s t r a t e d in F i g . 4. D e s p i t e
s o m e of t h e i n c o n s i s t e n c i e s i n S w i s h e r ' s a d a t a , a
reasonable estimate is made by extrapolating log K'
to z e r o a l u m i n u m c o n c e n t r a t i o n . T h e l i n e d r a w n i n
Fig. 4 is calculated using the following thermodynamic
data:

of s o l u t i o n of 1 w t p e t A1 a t 1600~ 2~ a n d t h e p a r t i a l
m o l a r h e a t of s o l u t i o n of a l u m i n u m f l s
A t t e m p t s to m e a s u r e e l e c t r o m o t i v e f o r c e s f o r m e l t s
c o n t a i n i n g m o r e t h a n a b o u t 1.4 wt p e t A1 f a i l e d . T h i s
i s a t t r i b u t e d to t h e p a r t i a l e l e c t r o n i c c o n d u c t i v i t y in
t h e ThOa(YaOs) e l e c t r o l y t e a t low o x y g e n p r e s s u r e s . In
m e l t s c o n t a i n i n g m o r e t h a n 1.4 wt p c t A1, t h e m e a s u r e d
electromotive forces continuously decreased.
The drop
i n t h e e l e c t r o m o t i v e f o r c e m a y h a v e b e e n d u e to t h e
p o l a r i z a t i o n of t h e C r - C r a O s e l e c t r o d e c a u s e d b y t h e
open circuit mass transfer accompanying electronic
c o n d u c t i v i t y . A t t e m p t s to d e p o l a r i z e t h e e l e c t r o d e b y
passing a reverse current were unsuccessful. After
passing the reverse current, the electromotive force

1800"C
I

1700~

1600"C

-3.0

2 A l ( / ) + { 02(g)= AhOs
AiF ~ = - - 4 0 1 , 5 0 0 + 7 6 . 9 1 T

(Ref. 11)

Ou(g) = O (1 wt p c t in F e )
AF ~ = - 28,000 -

0.69T

-4.0

(Ref. 11)

9
o

A l ( l ) = A1 (1 w t p c t in F e )
AF ~ = -27,600

(at 1600~

(Ref. 2 0 )

5 H ~ = -- 1 5 , 1 0 0 (at 1600~

(Ref. 23)

AiF ~ = - 1 5 , 1 0 0 -

1
48

McLEAN 8 BELL
PRESENT STUDY
I

50

6.67T

52

54

I / T x I0 ~

Fig. 5--e~AI) in liquid iron v s 1/T.

T h e f r e e e n e r g y c h a n g e f o r R e a c t i o n [13] i s , t h e r e f o r e ,
given by
AiF ~ = - 2 8 7 , 3 0 0 + 9 2 . 3 2 T

[15]

and log K by
log K = - 62,780/T + 20.17

[16]

A g r e e m e n t of t h e p r e s e n t w o r k a n d t h e p r e v i o u s l y d e termined values at the lower temperatures,

less than
1800~
with the calculated line is excellent. This
a g r e e m e n t s u p p o r t s b o t h t h e d e t e r m i n a t i o n of K a n d
t h e v a l u e s u s e d i n c a l c u l a t i n g t h e f r e e e n e r g y of s o l u t i o n of a l u m i n u m i n F e - A 1 a l l o y s , i . e . the f r e e e n e r g y

Table IV. The Solubility and Activity Coefficient of Oxygen in Fe-Ti

Alloys at 1600~

Titanium,
vet pct

Oxygen, wt pct

E, mv

-log fo

(Th02 Crucibles)
0.020
0.21
0.50
0.90

0.0099
0.0070
0.0051
0.0044

108 (111)
78 (III)
-60 (II)
-78 (1I)

0.0277
0.0207
0.0106
0.0086
0.0077
0.0086
0.0046
0.0033
0.0040
0.0045
0.0051
0.0040
0.0042
0.0050
0.0073
0.0098
0.0150
0.0207
0.0278
0.0401

127 (III)
74 (III)
72 (Ill, it)
50 (IIl, ii)
-25 (I1)
-45 (I|)
-43 (II)
-58 (11)
-60 (11)
-97 (11)
-130 (II)
-157 (11)
-160 (II)
-166 (II)
-210 (I1)
-245 (II)
-268 (I1)
-285 (II)

0.05
0.07
0.66
0.70

(ZrO2 Crucibles)
1900~
I

-9
-I0-

-II

1600%
I

[]

- 13

1800"C 170(PC
I
I

9 d'ENTREMONTet 01
9 McLEAN& BELL
Cl GOCKCEN8 CHIPMAN

c-~176

44

46

48

50
52
54
liT x IOs
Fig. 4--Log K v s 1 / T ( K = a~a~ ).
METALLURGICAL TRANSACTIONS

0 PRESENTSTUDY

- 14

~ ~,~
~

_J
|

"q
56

0.010
0.015
0.022
O.10
0.10
0.11
0.30
0.32
0.37
0.45
0.50
0.91
1.38
1.40
1.80
2.50
5.70
7.70
11.0
12.5

0.03
0.17
0.15
0.30
0.38
0.40
0.45
0.59
0.66
0.78
0.96
1.17
1.36

1.52
1.92

2.27
2.47
2.77

( ) indicates cell used.

VOLUME I,DECEMBER 1970-3407

Ti, wt. %
-I .0

0.01
I

0.1

I0

I
2.0

I
4.0

I
I
6.0
8.0
Ti, wt.%

I
I0.0

I000

500
zoo

~. -2.0

-I.0

I00 ~="

,o

50

20
-3.0

t
- 2.0

]
- 1.0

t
0

t
1.0

-2.0

10

10g(wt.% Ti)
Fig. 6--Solubility of oxygen in F e - T i alloys at 1600~
-3.0

0
Table V. The Activity of Titanium in Liquid Fe-Ti Alloys at 1600~
(Relative to Solid Titanium)

N,li

E, mv

aTi X 10~

-log "fTi

0.066
0.089
0.126
0.143

-210
-245
-268
-285

3.16
4.37
6.60
8.13

1.33
1.30
1.28
1.25

Fig. 7--Effect of titanium on the activity coefficient of oxygen

in liquid iron at 1600~

0.1

NTi

0.2

-I.2
would d e c r e a s e i m m e d i a t e l y , a t a r a t e of about 0.5
my p e r s e c . The a p p a r e n t l i m i t i n g oxygen p r e s s u r e
at 1600~ f o r which ThO2(YzOs) b e h a v e s a s a p r e d o m i n a n t l y i o n i c c o n d u c t o r is about 1.0 10 "~a a t m , c o r r e s p o n d i n g to about 0.3 p p m o x y g e n in unalloyed i r o n .

O
I
12.0

j, J

-I.5
J
o
P.4

J s

-I.4

Fe-Ti-O
The s o l u b i l i t y of oxygen in F e - T i a l l o y s e q u i l i b r a t e d
with a t i t a n i u m oxide p h a s e at 1600~ is p r e s e n t e d in
T a b l e IV and p l o t t e d in F i g . 6. The s o l u b i l i t y is a m i n i m u m of about 0.004 wt p c t a t 0.9 wt pct Ti. T h e s e r e s u l t s a r e in f a i r a g r e e m e n t with t h o s e of Wentrup and
H i e b e r 1 and Hadley and D e r g e . z The s o l u b i l i t i e s r e p o r t e d by Chino e t a l . , s < 0.001 wt pct O at 0.1 p ct Ti,
a r e s i g n i f i c a n t l y l o w e r than t h o s e m e a s u r e d in the
p r e s e n t wo r k .
In F i g . 7, log fo is p l o t t e d v s wt p c t Ti. Log fo is
not a l i n e a r function of t i t a n i u m c o n te n t o v e r the e n t i r e c o m p o s i t i o n r a n g e s t u d i e d . The v a l u e of e (Ti) at
infinite dilution is - 1.12. The c o r r e s p o n d i n g v a l u e of
Eo(Ti) is -- 222.
F o r a l l o y s containing o v e r 5 at. p c t Ti, the a c t i v i t y
of t i t a n i u m is c a l c u l a t e d u s i n g Eq. [6], and the r e s u l t s
a r e p r e s e n t e d in Table V. In o r d e r to e s t i m a t e the
v a l u e of ~Ti, the e x p e r i m e n t a l r e s u l t s a r e p lo tt ed in
Fig. 8 in a c c o r d a n c e with D a r k e n ' s ~I q u a d r a t i c f o r m a l i s m . The c o m p o s i t i o n r a n g e of this i n v e s t i g a t i o n is too
s m a l l to t e s t the v a l i d i t y of the q u a d r a t i c f o r m a l i s m
f o r t h i s s y s t e m . H o w e v e r , the r e s u l t s give a f a i r l i n e a r r e l a t i o n s h i p with C~FeTi e q u a l to a p p r o x i m a t e l y
- - 0 . 6 . E x t r a p o l a t i n g back to i n f i n i t e dilution of t i t a n i um, the v a l u e of ~2Ti is 0.038 r e l a t i v e to s o l i d t i t a n i u m .
The v a l u e of ~TiO c a l c u l a t e d , u s i n g an e q u i v a l e n t e x p r e s s i o n to Eq. [12], is - 96. The v a l u e s of the v a r i ous p a r a m e t e r s d e s c r i b i n g the t h e r m o d y n a m i c s of the
F e - T i - O s y s t e m at 1600~ a r e s u m m a r i z e d in Table
IH.
The v a l u e s of the co(Ti} ( - 222) and ~Ti (0.033) d e t e r m i n e d in the p r e s e n t w o r k a r e not in good a g r e e m e n t
3408-VOLUME I,DECEMBER 1970

-I.5
1.0

I
0.8

I
0.6

N2
Fe

Fig. 8--Log TTi (solid reference) in F e - T i alloys at 1600~

with t h o se e s t i m a t e d by Chipman, s Ti) = - 37 and ~Ti
= 0.011. H o w e v e r , C h i p m a n ' s v a l u e s w e r e only e s t i m a t e d f r o m the r e s u l t s of Hadley and D e r g e s i n c e the
a c t i v i t i e s w e r e not m e a s u r e d d i r e c t l y . C o n s i d e r i n g
the a s s u m p t i o n s which w e r e n e c e s s a r y f o r C hi pma n
to c a l c u l a t e ~2Ti and c o(Ti)., this d i s a g r e e m e n t is u n d e r standable.
G E N E R A L DISCUSSION OF F e - X - O SYSTEMS
The a u t h o r h as d e t e r m i n e d the s o l u b i l i t y of oxygen
and the a c t i v i t i e s f o r the F e - C r - O , .4 F e - V - O , 16
F e - B - O , 18 F e - A I - O , and F e - T i - O s y s t e m s . C e r t a i n
c h a r a c t e r i s t i c s and t r e n d s f o r t h e s e s y s t e m s a r e d i s c u s s e d below.
In Fig. 9, l o g Y o / ~ is p l o t t ed vs a t o m f r a c t i o n of
a l l o y i n g e l e m e n t ( N x ) . As N x a p p r o a c h e s z e r o , the
f i r s t o r d e r i n t e r a c t i o n c o e f f i c i e n t E ~ ) a p p e a r s to be
a r e a s o n a b l e r e p r e s e n t a t i o n of the e x p e r i m e n t a l r e s u l t s . H o w e v e r , in al l the s y s t e m s i n v e s t i g a t e d t h e r e
is e v e n t u a l l y a m a r k e d d e v i a t i o n f r o m the s i m p l e l i n e a r b e h a v i o r . Lupis and E l l i o t t 24 h a v e i n t r o d u c e d g e n eralized interaction coefficients incorporating higher
t e r m s . F o r the s o l u t i o n s under d i s c u s s i o n , N o a p p r o a c h i n g z e r o , the a c t i v i t y c o e f f i c i e n t can be r e p r e s e n t e d by
METALLURGICAL TRANSACTIONS

In/o

Co<X>

+ pF >

It,,]

+ ...

In g e n e r a l the use of a s e c o n d o r d e r i n t e r a c t i o n c o e f f i c i e n t pc(X) along with r (X) d o e s not a d e q u a t e l y r e p r e s e n t the e x p e r i m e n t a l c u r v e s in Fig. 9. In g e n e r a l ,

t h r e e o r e v e n m o r e t e r m s a r e n e c e s s a r y to d e s c r i b e
the r e s u l t s . The use of h i g h e r i n t e r a c t i o n p a r a m e t e r s
is not p a r t i c u l a r l y useful s i n c e the data a r e b e s t d e s c r i b e d by the e x p e r i m e n t a l c u r v e s in Fig. 9 and
h i g h e r o r d e r t e r m s do not y i e l d any i n f o r m a t i o n c o n c e r n i n g the n a t u r e of the s o l u t i o n . The only useful o b s e r v a t i o n which can be m a d e f r o m the h i g h e r t e r m s is
that f o r a l l the s y s t e m s i n v e s t i g a t e d pc(X) is p o s i t i v e ,
i.e. a p o s i t i v e c u r v a t u r e .
In T a b l e VI the v a l u e s of r (X) a r e l i s t e d along with
AFx2os / 3 ; the o x i d e X2Os w a s c h o s e n s i n c e it is the
only o x i d e p h a s e which e x i s t s f o r a l l the a l l o y i n g e l e m e n t s c o n s i d e r e d h e r e . As shown in Fig. 10, the m a g nitude of c ~ ) i n c r e a s e s with i n c r e a s i n g v a l u e of
- A F x 2 0 3 / 3 . H o w e v e r , t h e r e d o e s not a p p e a r to be any
predictable relationship between these quantities. Seve r a l s o l u t i o n m o d e l s have b e e n p r o p o s e d to p r e d i c t the
v a l u e of Eo(X) f r o m the b e h a v i o r of the b i n a r y s o l u t i o n s
o r s t a b i l i t y of the oxide phases.ZS'ze None of t h e s e m o d e l s p r e d i c t s c ~ ) with s u f f i c i e n t a c c u r a c y f o r a l l the
s y s t e m s studied.
Although t h e r e is no d i r e c t r e l a t i o n s h i p b e t ween c o

-0.5

-I.0

-I.5

- 500

oi,

o'2

0'3

0:4

ATOMFRACTION ( Cr,V, B, Ti or AI )
Fig. 9--Effect of Cr, V, B, Ti, and AI on the activity coefficient of oxygen in liquid Fe-X-O alloys.

Table VI. Fe-X-O Solutions at 1600~

,~ox )
Alloying AFX203/3
Elements kcal/mole O*, ppm
A1
Ti
B
V
Cr

-85.8
-81.6
-66.2
-62.0
-51.9

6
40
80
180
270

N~
0.002
0.01
0.03 to 0.05
0.03
0.07

Calculated
Quasichemical
Experimental z = 2 z = 8
-433
-222
-115
-29.0
-8.0

-257 -18
-186 -17
-35 -8.6
-25 -3.6
-17 -2.5

O - minimumoxygencontent.
N - atom fraction of alloyingelementat oxygensolubilityminimum.
METALLURGICAL TRANSACTIONS

Io
-400

I
I
I

-30O
A

a< 0
~U

/
/o

-200

/
o

- I00

/
/

_
o

__

1_
Io

~--o-r"
20

(AFx2o/3

""~

30
-AFFe

I
40

I
50

60

0 1, kcol/mole

Fig. 10--The effect of oxide stability on E~X) (X is A1, Ti, B,

V, or Cr).
and the s t a b i l i t y of the oxide, the g e n e r a l finding that
%(X) b e c o m e s m o r e n e g a t i v e as the s t a b i l i t y of the
oxide i n c r e a s e s can be r o u g h l y u n d e r s t o o d in q u a l i t a tive t e r m s . Oxygen in F e - X - O s o l u t i o n s w i l l l o w e r its
c h e m i c a l p o t e n t i a l r e l a t i v e to an F e - O s o l u t i o n when
they a r e n e a r a t o m s which f o r m o x i d e s s t a b l e r e l a t i v e
to FeO. This l e a d s to c l u s t e r i n g of o x y g e n a t o m s
a r o u n d the s o l u t e X. In a r e c e n t p u b l i c a t i o n , F r u e h a n
and R i c h a r d s o n 27 p r e s e n t e d e v i d e n c e i n d i c a t i n g that an
oxygen a t o m m a y i n t e r a c t s t r o n g l y with only one o r
two of its n e i g h b o r i n g s o l u t e and s o l v e n t a t o m s . The
r e l a t i v e l y l a r g e v a l u e s of Co(X) l i s t e d in T a b l e VI can
be p r e d i c t e d f r o m the q u a s i c h e m i c a l m o d e l of Alcock
and R i c h a r d s o n 2~ only if one a s s u m e s a low v a l u e , e.g.
one o r two, f o r the n u m b e r of a t o m s i n t e r a c t i n g with
an oxygen a t o m . In Table VI the v a l u e s of co(X) c a l c u l a t e d f r o m the q u a s i c h e m i c a l m o d e l , u si n g Eq. [18],
a r e l i s t e d a s s u m i n g the n u m b e r of a t o m s i n t e r a c t i n g
with an oxygen (z) to be two o r eight.

yo(in Fe)
-2.5

[18]

In the c o m p u t a t i o n , the d i f f e r e n c e b e t w e e n f r e e e n e r g y
of an F e - O and X - O i n t e r a c t i o n was e s t i m a t e d by the
d i f f e r e n c e in the f r e e e n e r g y of f o r m a t i o n f o r the o x ides p e r m o l e of oxygen. It should be noted that the
use of the q u a s i c h e m i c a l r e l a t i o n s h i p s f o r z e qua l to
2 is an a p p r o x i m a t i o n s i n c e the n u m b e r of m e t a l m e t a l i n t e r a c t i o n s should be the usual n u m b e r , b e t w e e n
8 and 12. This a p p r o x i m a t i o n does not a f f e c t the g e n e r a l findings s i n c e the e n e r g y of the m e t a l - m e t a l i n t e r a c t i o n s is s m a l l r e l a t i v e to the m e t a l - o x y g e n i n t e r a c t i o n s . H o w e v e r , d e s p i t e t h e s e a p p r o x i m a t i o n s it is
c l e a r that the n u m b e r of m e t a l - o x y g e n i n t e r a c t i o n s
p e r a t o m of o x y g e n m u s t be s m a l l in o r d e r to have the
r e l a t i v e l y l a r g e v a l u e s of r (X) found e x p e r i m e n t a l l y .
In g e n e r a l , the e x p e r i m e n t a l v a l u e of co(X) is s l i g h t l y
h i g h e r than the v a l u e c a l c u l a t e d f o r z = 2. Using a
v a l u e of z = 8, s i g n i f i c a n t l y s m a l l e r v a l u e s of-%(X) a r e
c a l c u l a t e d c o m p a r e d to those f o u n d e x p e r i m e n t a l l y .
The s m a l l n u m b e r of m e t a l - o x y g e n i n t e r a c t i o n s m a y
be v i e w e d as the f o r m a t i o n of a m o l e c u l a r s p e c i e as
p r o p o s e d in the s o l u t i o n m o d e l of Belton and Tankins, ze
o r s i m p l y as a c l u s t e r i n g with all the bonding e n e r g y
VOLUME 1,DECEMBER 1970-3409

wt.% (Cr,V,B, Ti or A1 )
0.01
I

0.1

1.0

I0.0

100

5000
2000
I000
500

Cr

-I.O

2O0
IO0 ="
50 o"

1r

~ -2.0

20
I0

-3.0

5
2

-4.0

-20

-10
0
10
2.0
109 (wt.%Cr.V,B,Ti oral)
Fig. l l - - E f f e e t of alloying e l e m e n t s on oxygen solubility in
liquid s t e e l at 1600~ (B at 1550~

a n d E(Ti) = - 2 2 2 (e (Ti) = 1.12). T h e a c t i v i t y c o e f f i c i e n t

of a l u m i n u m a t i n f i n i t e d i l u t i o n in l i q u i d i r o n i s 0.021
w h i l e t h a t of t i t a n i u m ( r e l a t i v e to s o l i d t i t a n i u m ) i s
0.038.
The equilibrium constant (solubility product for pct
A1 - - 0) f o r a l u m i n u m d e o x i d a t i o n i s 5 . 6 x 10 -14 a t
1600~
T h e ThOa(Y203) e l e c t r o l y t e b e h a v e s p r e d o m i nantly as an oxygen ion conductor in melts containing
up to a b o u t 1 . 4 w t p c t A1, w h i c h c o r r e s p o n d s to a n o x y g e n p a r t i a l p r e s s u r e of 10 -16 a t m o r 0 . 3 p p m O i n u n alloyed iron.
There appear to be general trends in certain chara c t e r i s t i c s of F e - X - O s o l u t i o n s , w h e r e X i s C r , V, B,
Ti, o r A1. As t h e s t a b i l i t y of t h e o x i d e of t h e a l l o y i n g
e l e m e n t i n c r e a s e s , e~x) b e c o m e s m o r e n e g a t i v e , t h e
minimum oxygen solubility becomes less, and the mini m u m o c c u r s a t a l o w e r c o n c e n t r a t i o n of t h e a l l o y i n g
element.
ACKNOWLEDGMENTS

in o n e o r two b o n d s . In e i t h e r c a s e t h e e f f e c t i s to s u b s t a n t i a l l y i n c r e a s e t h e p r o b a b i l i t y of a n X - O i n t e r a c t i o n , t h u s l o w e r i n g t h e c h e m i c a l p o t e n t i a l of o x y g e n i n
s o l u t i o n a n d g i v i n g r i s e t o h i g h v a l u e s of eo(X) .
In F i g . 11, t h e o x y g e n s o l u b i l i t y f o r t h e F e - X - O s y s t e m s s t u d i e d is p r e s e n t e d . F o r a l l t h e s y s t e m s s t u d i e d
t h e a l l o y i n g e l e m e n t s d e c r e a s e t h e s o l u b i l i t y to a m i n imum oxygen content and the solubility increases with
f u r t h e r i n c r e a s e i n t h e a l l o y i n g e l e m e n t . As t h e c o n c e n t r a t i o n of t h e a l l o y i n g e l e m e n t i n c r e a s e s , s o d o e s
its activity; however, for all systems studied, the all o y i n g e l e m e n t d e c r e a s e s t h e a c t i v i t y c o e f f i c i e n t of
oxygen. Therefore, a minimum in the oxygen solubili t y o c c u r s . C e r t a i n t r e n d s c o n c e r n i n g t h e oxygen" s o l u b i l i t y m i n i m u m a r e a p p a r e n t f r o m F i g . 10 a n d T a b l e
VI. T h e m i n i m u m o x y g e n c o n t e n t (O*) d e c r e a s e s a s
t h e s t a b i l i t y of t h e o x i d e i n c r e a s e s .
Also, the alloy
c o m p o s i t i o n a t w h i c h t h e m i n i m u m o c c u r s (N*) d e c r e a s e s w i t h i n c r e a s i n g s t a b i l i t y of t h e o x i d e . St.
P i e r r e a n d B l a c k b u r n a~ h a v e d e r i v e d a r e l a t i o n s h i p
b e t w e e n t h e f i r s t - o r d e r i n t e r a c t i o n c o e f f i c i e n t s ( e !x)
a n d Eo(x)) a n d N*. T h e i r r e l a t i o n s h i p a s s u m e s that''~the
activity coefficients are adequately described by firstorder interaction coefficients and that the equilibrium
oxide phase at the minimum has a stoichiometric comp o s i t i o n . T h e y h a v e s h o w n t h a t if %(x) << 0, w h i c h i s
the case for all systems studied,
N* -~ -

- r

[19]

~o~)
w h e r e r i s t h e r a t i o of m e t a l t o o x y g e n i n t h e o x i d e
p h a s e . A s d i s c u s s e d p r e v i o u s l y , a s t h e v a l u e of - ~o(X)
i n c r e a s e s , t h e c o m p o s i t i o n N* d e c r e a s e s .
This observ a t i o n i s c o n s i s t e n t w i t h E q . [19]. It s h o u l d b e n o t e d
that in the author's investigations these quantities
w e r e n o t d e t e r m i n e d i n d e p e n d e n t l y , t h e r e f o r e , E q . [19]
w i l l n o t c o n s t i t u t e a n i n d e p e n d e n t c h e c k of t h e r e s u l t s .
SUMMARY
T h e s o l u b i l i t y of o x y g e n i n F e - A I a n d F e - T i a l l o y s
i s a m i n i m u m of a b o u t 6 p p m a t 0 . 0 9 wt p c t Al, a n d
40 p p m a t 0.9 w t p c t Ti, r e s p e c t i v e l y a t 1600~
The
i n t e r a c t i o n c o e f f i c i e n t s a r e : eo(AI) = - 4 3 3 (e~AI) = 3 . 9 0 )

3410-VOLUME I,DECEMBER 1970

T h e a u t h o r w i s h e s to t h a n k L. J. M a r t o n i k f o r h i s
e x c e l l e n t a s s i s t a n c e in p e r f o r m i n g t h e e x p e r i m e n t s ,
E. T. T u r k d o g a n a n d L. S. D a r k e n f o r h e l p f u l d i s c u s s i o n s , G. W. M o m e y e r a n d h i s a s s o c i a t e s f o r a l u m i n u m a n d t i t a n i u m a n a l y s e s , a n d J. F . M a r t i n a n d h i s
associates for oxygen analyses.

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2-4.

METALLURGICAL TRANSACTIONS