S e c t i o n I: B a s i c a n d A p p l i e d R e s e a r c h

T h e r m o c h e m i c a l Properties of
Iron-Rich Liquid Solutions Containing
Oxygen and Aluminum
D. B o u c h a r d
Insitute for Materials Research
McMaster University
Hamilton, Ontario, Canada, L8S 4L7
and
C.W. B a l e
C e n t r e d e R e c h e r c h e en Calcul T h e r m o c h i m i q u e
Ecole P o l y t e c h n i q u e d e Montreal
C.Po 6 0 7 9 , Succ. A, M o n t r e a l , Quebec, C a n a d a , H3C 3 A 7

(Submitted June 27, 1994; in revised form November 27, 1994)

Thermochemical properties of iron-rich liquid solutions containing oxygen and aluminum were as-
sessed by simultaneously considering experimental data reported in the Fe-O, Fe-Al, and Fe-AI-O
systems. Three models were investigated to describe the liquid iron-based solution. One model con-
sidered the species Fe, AI, and O while the other two were cluster models. In the first of these cluster
models, the species Fe-AI-O-AIO were considered, and in the second, the species AI20 was added.
Among the three models, the properties of the liquid solutions were satisfactorily described with both
cluster models. The model containing the species Fe-AI-O-AIO-AI20 could however provide a closer
picture of the configuration of the atoms in the melt.

1. Introduction phase as a substitutional solution but distinguished themselves

The Fe-O-A1 system plays a prominent role in steel making. To
prevent the formation of blowholes during solidification of in-
gots, oxygen contents must be kept to a minimum, and alumi-
num is routinely added to act as a deoxidizer. Alumina
inclusions are commonly formed following aluminum addi-
tions, and their amounts must be controlled as they can block
the tundish nozzles and prevent the liquid metal from flowing
freely during continuous casting operations. These inclusions
can also produce deleterious effects on the mechanical proper-
ties of finished products, and a great deal of effort is invested
by the steel industry to produce clean steels. A set of thermo-
chemical parameters describing iron-rich liquid solutions con-
taining aluminum and oxygen would thus be very useful to
forecast the formation of alumina inclusions and the residual
amounts of oxygen or aluminum in solution.
In this work, published experimental data in the Fe-O, Fe-AI,
and Fe-AI-O systems were analyzed in order to optimize the
values of these thermochemical parameters. In the ternary Fe-
A1-O liquid solutions, very strong interactions between alumi-
num and oxygen atoms have been reported. For example, the
value of the interaction parameter, ea~,O,calculated by Fruehan
from his experimental measurements at 1600 ~ was quoted to
be -433 [70Fru2]. Such strong interactions could have sensi-
ble effects on the configuration of the atoms in the melt.
In the present evaluation, three different configurational mod-
els were compared on the basis of their ability to reproduce the
experimental information. All three models treated the liquid
by the number of species. In the first model, only three species
were considered: Fe, A1, and O. The second model assumed an
extra species, A10, was present. The last model assumed that
the species Fe, A1, O, AIO, and AI20 were simultaneously pre-
sent.
Nonlinear programming techniques were employed to opti-
mize the parameters. Three distinct matrices containing the
mathematical relations describing the phase equilibria data
were built to constitute the constraints of the three models. Ob-
jective functions were also defined to provide a least square fit
of the experimental data. and the variables contained in the ma-
trices were simultaneously optimized using an iteration proce-
dure.
2. C o n s t r u c t i o n o f t h e M o d e l s f r o m
Phase Equilibrium Data
The activity coefficients of the solutes of the liquid phase were
expressed using the unified interaction parameter formalism
[86Pel, 90Bali. Although these coefficients could be expressed
with Margules-type polynomials, the notation of the formal-
ism is similar to the one the steel industry has used over the last
forty years and was for this reason considered more appropri-
ate. In this formalism, the Raoultian activity coefficients are
formulated as such:

I(~ Journal of Phase Equilibria Vol. 16 No. 1 1995

 Basic and Applied Research: Section I

N N N
RIln(Po2) = RTIn(Xo) + R71n('yo) + I (Eq 8)
Iny = lnYsolvent+ ln~ + E ~tJx: + ~ eiJk XIXk + E ~JktXjXkXt
1:1 j ,k=-1 j ,k,l= 1
Equation 7 describes a thermodynamic equilibrium while Eq 8
+ ... (Eq l) describes the experimental observation associated to the equi-
where librium. The variable, I, possessing energy units and whose
value can be positive or negative, implies that the experimental
N
1 2 observation is contained within an uncertainty bracket. Usage
lnTsolvent: - "2 E ~jkXjX* - -3 E EjktXXkX1 of uncertainties in relations describing experimental observa-
j,k=-I j,k,l= l tions related to thermodynamic equilibrium has been reported
N
before [73Gor, 73Rao, 74Rao, 77Gor, 84Ber]. Each experi-
N mental result yields a relation such as Eq 8 constituting only
3 part of the matrix describing a model. Those belonging to the
-- -4 E E j k l n ~ j X k X t X m - - " " (Eq 2)
j,k,l,m=l Fe-AI binary and Fe-AI-O ternary were also included before
optimizing the values of the interaction parameters.
In these two expressions, N is the number of solutes, and i = 1,
2 ..... N. The activity coefficient of solute i at infinite dilution is 2.2 Fe-AI S y s t e m
denoted by ~, and X refers to the mole fraction. The first-order
Belton and Fruehan [69Bel] determined the activities of alumi-
interaction parameters appear as Etj; Ei,j, k and ei,j,k, l are the num in liquid iron over the entire composition range at 1600 ~
higher-order parameters. As many parameters as desired can using a Knudsen cell coupled to a mass spectrometer. Only the
be utilized, but one or two are usually sufficient for most pur- results where aluminum was the solute were considered in the
poses. The order of the subscripts is irrelevant: present evaluation (XAI < 0.5). A set of equations similar to the
following one was generated for each of their measurements:
I~lj = EjI
RTln (aA1) = RTln (XAI) + RTln (Tn]) + I (Eq 9)
Eij k = E tkj = Ejt k =" elk ` = EkiJ = Ekj i
where aA1 is a reported aluminum activity relative to pure liq-
Ezjkl : Ejikl "= Ekijl =" . . . uid aluminum, Xal is the corresponding aluminum mole frac-
tion, TAX is the aluminum activity coefficient, R is the gas
Eijj : Ejj i : Ejlj (Eq 3) constant, Tis the absolute temperature, and I is the uncertainty
The temperature dependence of the parameters was expressed in the measurement.
as: Enthalpies of mixing of aluminum in liquid iron from cal-
A orimetric measurements at 1600 ~ [67Woo] were also in-
e = -~ + B (Eq 4) cluded in the model. The Gibbs-Helmholz equation:

and for the activity coefficient at infinite dilution as:

~ T --AnuxHAl
ln~ = A
y +B (Eq 5) TZ (Eq 10)

2.1 Fe-O S y s t e m with G ~ = RTInTA1, was used to relate the interaction parame-
ters to the measured partial molar enthalpies of mixing AmixHAl.
There are numerous studies on the solubility of oxygen in liq- Another set of equations was thus formulated and added to the
uid iron. The results ofGokcen [56Gok], Floridis and Chipman matrix, each equation expressed as follows:
[58Flo], and Tankins et al. [64Tan] were considered. In these
experiments, equilibrium was reached when the chemical po- (oqlnTA' "~
tential of gaseous oxygen equaled that in the liquid iron: ArmxHA1= - R T 2 [ - - ~ J + I (Eq 11)
1
lt52 = la~) (Eq 6) 2.3 Fe-AI-O S y s t e m

from which As mentioned previously, three thermodynamic models were

RTIn (Po2) = RTln(Xo) + RTln(7o)
Experiments to determine the oxygen solubilities in liquid
iron, Xo, at corresponding oxygen partial pressures in the gas,
Po2, and temperatures, T, would yield the necessary informa-
tion to calculate the interaction parameters in the activity coef-
ficients. When a series of measurements is carried out to
determine these quantities, uncertainties are introduced in Eq
7. In order to take these into account, this equation can be
modified as follows:
evaluated to describe the experimental data in this ternary so-
(Eq 7) lution. The results of each model are discussed and compared.
The experimental data of Gokcen and Chipman [53Gok],
McLean and Bell [65Mcl], and Fruehan [70Fru2] were em-
ployed.
2.3.1 Fe-AI-O M o d e l
Alumina solubility measurements in liquid iron by Gokcen
and Chipman [53Gok] as well as those by McLean and Bell
[65Mcl] were carded out at several temperatures in pure alu-
mina crucibles and oxygen activities fixed by known H2/H20

Journal of Phase Equilibria Vol. 16 No. 1 1995 17

Section I: B a s i c and Applied Research

ratios. Fruehan measured the oxygen activities of various iron hAlo

solutions in pure alumina crucible with a zirconia solid electro- XA10-- (l --hAlO) (Eq 17)
lyte galvanic cell. His measurements were restricted to 1600
~ where the quantities with the primes are the gross number of
The oxygen activities, relative to pure gaseous diatomic oxy- moles and those without are the actual number of moles in so-
gen at 1 atmosphere, the alloy compositions, and the tempera- lution. The latter were variables whose values also had to be
tures being reported in these three studies, each experimental optimized.
measurement yielded an equation such as:
The reaction of the formation of the A10 clusters:

RTIn (Po2) = RT ln(Xo) + RT In(To) + I (Eq 12) A I ( X ~ + O(XdO = A I O ( X ~ (Eq 18)

also permilted a new set of equations to be added. Each of these

Aluminum activities from these studies were also calculated, equations is given by the expression of the standard Gibbs en-
relative to pure liquid aluminum, from the known oxygen ac- ergy of the reaction:
tivities and the standard Gibbs energy of formation of alumina
calculated from J A N A F [85Cha]: .( Xalofalo )
A 1 + B l T = --RTln[XA----1-~N-~ofo (Eq 19)
3
2AI(I) + ~-O2(g ) = A1203(s ) (Eq 13)
where A 1 and B 1 are variables a n d f is the Henrian activity co-
and additional equations illustrated by: efficient of solute i.
The objective function in this model was also defined to mini-
RT ln(aAl ) = RTln (XAj) + RTIn (TA1) + I (Eq 14) mize the sum of the square of the uncertainties and was thus ex-
actly the same as Eq 16.
were added to the matrix.
2.3.3 Fe-AI-O-AIO-AI20 M o d e l
Other equations were formulated to constrain the products of
the aluminum and oxygen activities at values consistent with The assumption that two clusters were present only brought
the standard Gibbs energy of Eq 13 calculated from the slight modifications to the equations thus far presented, and a
J A N A F [85Cha] compilation: new matrix could easily be built for this thermodynamic
model. Equations 1 to 15 were unmodified, and the number of
AG~ [(Xo) 3/2 (To) 3R (XAI)2 (TA1)2 ] + I (Eq 15) solutes, N, in Eq 1 and 2 was increased to 4 to account for the
presence of AI20. Equation 17 was replaced by new mass bal-
Equations 1 to 15 illustrate the constraints of the first program. ance equations formulated as follows with respect to one mole
The objective function, Z, needed to complete this model was of atoms of solution:
chosen to minimize the sum of the square of the uncertainties.
Weights were also introduced by multiplying each uncertainty (tlA1 -- rtAIO -- 2t/Al 2 O)
by a factor, W. The objective function was thus: XAI
(1 - ?IA10-- 2nAl20)
tt

Min Z = ' ~ WI(1,)2 (Eq 16)

(r/5 - hAlO - 2,tAi,O )
1=1
X~ = ( 1 - hA1o -- 2nal,O;
where u represents the total number of experimental observa-
tions.
hAlO
2.3.2 Fe-Al-O-AlO M o d e l XAIO
(1 - hAlo - 2nA120)
A new matrix was constructed for this thermodynamic model.
Equations 1 to 15 still applied so that only minor modifications t/Al~O
to the previous matrix were made. The number of solutes, N, in " (gq 20)
XAITO= (1 - hAlo - 2rIAlTO)
Eq 1 and 2 was increased by one to account for the presence of
the A10 species. Supplementary equations were also included. The quantities with the primes are the gross number of moles;
The mole fractions were expressed according to the following those without are the actual number of moles in solution.
linear equations pertaining to the mass balances with respect to
one mole of atoms of solution: The equations describing the Gibbs energy of formation of the
A10 clusters (Eq 19) were unmodified and left in the matrix as
t
(r/Al -- r/AiO) such. A second set of equations was added to account for the
XAI- (1 _ hAlo) formation of the AI20 clusters:
2AI(X,)r + O(Xoc) = A120(X4"c) (Eq 21)
p
(n 0 -- nAtO)
XO - with each of these equations formulated as:
(1 - ?IAIO)

18 Journal of Phase Equilibria Vol. 16 No. 1 1995

 Basic and Applied Research: Section I

2.2 0.7 ' i ' i . i , i , i ' i ' i ' i , I '

o [58F10] A//~f.-"" o [58FIo] T ~ 1550~ .iv /
9 [64Tan] ~ ' " 0.6 9 [64Tan] / ~
A 15600k] = . / . " "~ o a [56Gok] /~_~""
2.1 ..... O p t t m t z a t t o n #1 ..~"
""" I 0.5 .... O p t i m i z a t i o n #1 //,~Ir/~ o
..... opt ..... tin. ~ ~f:" 9~ .... O p t t m t z a t t o n #2 /~.o
- - O p t i m i z a t i o n #3 ~ u
~ 0.4 - - Optimization//3 f
r~
o 2.0 < .-~9
.2

002
1.9
0,1

/ 0.0 , i , i . i , i . i , i , i , ~ . t ,

0.0 0.5 1.0 1.5 2 0 2.5 3.0 3.5 4.0 45 5.0

1.8
5.0 ,'.1 ,'.3 ;, ,'.5 56 Po2/2 9 10-5
10000/T (K)
Fig. 2 Solubility of oxygen in liquid iron as a function of oxygen
Fig. 1 Logarithm of the equilibrium constant as a function of the activity at 1550 ~ Pure diatomic gaseous oxygen at 1 atm stand-
inverse temperature for the reaction 1~O2(g) = O(X#% ard state.

Table 1 Optimized Interaction Parameters

0.4 . . . . I . . . . I . . . . t
OptimizationNo. 1 Optimization No. 2 Optimization No. 3
9 [69Bell T = 1600 ~

/
In'/~,a = - 7 7 7 ~ 0 / T + I 0 lny~ - - 7 5 9 6 7 / / ' + 1 2 In~ = -7867 1//'+ 1 3
--- Optimization #1 ln'~u = - 1 8 140 0 : f + 5 0 In~) = - 1 5 280 0 / T + 3 5 ln~) = - 1 6 240 0 / T + 4 0
9~ 0,3
- - - Optlmtzatton #2 ~'AI,~J = 6 4 8 9 1/1 + I 2 EAI,m - 3802 7 I f + 0 4 EAI,,~ = 7305 5IT + 0 4
J eA1,Al,a~ = 12 191 2 / I cAI,Al,,~ = 19 183 I/T ~:AI,AI,AI = 10 794 5/F
-- Optimization #3 vAl,o = - 869 414 OIT E:AI ,an = ~ . 8 6 AG'~ = - 5 3 9 413 0 + 161 5 T
~:AI,:Io = 18 9 6 9 9 6 0 0 / T AG~ = - ~ . 2 6 716 3 + 102 3T AG~=-ISI 21

"i 02
AG~ (J/tool) is the standard Gibbs energy of formation for the reaction: AI(1) +
1/202(g) = AIO(Xur AG02 is the standardGibbs energyof formationfor the reac-
0. I
tion: 2Al(I) + 1/202(g)= AIzO(X,]).Temperaturesare in degrees kelvin.

9 I i i i h
0.0
0.0 0.1 0.2 0.3 0.4 0.5 The model with the Fe-O-AI species yielded a linearly con-
A l u m i n u m , Mole Fraction
strained nonlinear program while the other two programs were
Fig. 3 Aluminum activities in liquid iron at 1600 ~ Pure liquid nonlinearly constrained. The variables in the models were op-
aluminum standard state. timized using iteration procedures [88Bro]. The interaction
parameters and the standard Gibbs energy of formation of the
clusters are listed in Table 1. Figures 1 to 8 illustrate the results

A2+ B2T:-RTIn(.
t , ,Xolo)
XAIzOfAI20 / (Eq 22)
of the calculations performed with the optimized data. The
curves labeled Optimization No. 1,2, and 3 refer to the Fe-AI-
O species model and the one- and two-cluster models, respec-
tively.
A2 and B 2 are new variables. The objective function for this
model was identical to Eq 16. 3.1 Fe-O System

3. Results and Discussion The curves shown in Fig. 1 and 2 agree well with the experi-
mental data on the oxygen solubility in liquid iron. The Fe-O
The equations presented in the previous section constituted binary phase was treated as a Henrian solution. This agrees
three distinct programs whose standard notations can be ex- with the conclusion of Gokcen [56Gok] and Tankins et al.
pressed as: [64Tan]. Floridis and Chipman [58F1o] reported that the pres-
ence of an interaction parameter, Co,o, was justified. Such apa-
minimizef(x), xeR" rameter would not sensibly improve the fit of the experimental
subject to data in Fig. 2 as the relationship between mole fractions and
gj(x) = 0, j = 1,2 ..... m (Eq 23) oxygen activities appears linear.

where f(x)=flxl,x2,,..x,,) is the objective function, x are the 3.2 Fe-AI System
variables, and n is the total number of variables. R,, is an n-di-
mensional Euclidian space. The constraints are denoted by In Fig. 3, activities calculated with the optimized parameters
gl(x) = gj(xl,x2,...Xm), and m is their total number. can be compared to the experimental values. The calculated

Journal of Phase Equilibria Vol. 16 No. 1 1995 19

S e c t i o n I: B a s i c and A p p l i e d R e s e a r c h

-20.0 i i i i -1.0
o T I_- 1866 aC I [53Gokl
' i
9 [67Woo] Jr" ~ &9 TT == 17601823~176[53Gok]165McL] - - Optnmization ~ # 1
..... Opttmtzatton# 1 9
..... Optimization #2 ~ " o O T = 1695 ~ [53Gok] / _ \
-30.0 -1.5 9 T = 1723 eC [65McL] / /~, \
- - Optimizatton #3 ~7"
m9
T = 1600~ ~ 9
~I -40.0 -2.0 "~

L ~ . . j I / 9
" ~ ' ~ -50.0

o
-60.0 -3.0 ' ~ ~ ~ v ~ ~

v
-70.0
0.0 0'.1 0'2 014
0'3 "3"53.0 ~ -21.5 ' -21.0 ' -II.5 -II.0 -01.5 ' 01.0 ' 5
A l u m i n u m , mole fractions log(Aluminum, Weight Percent)

Fig. 4 Partial enthalpies of mixing of aluminum in liquid iron as Fig. 5 Alumina solubility in liquid iron at various temperatures
a function of composition. considering the presence of two solutes, A1 and O.

tions [68StE 74Fel, 74Hon, 77StP]. Considering the dissolu-

-I.0 ' i 9 i ' i i i i tion of alumina in liquid iron, the following is obtained:
o T = 1866eC [53Gok]
9 l 1823 ~ [65MoLl -- Optimization #2
t~ T = 1760~ [53Gok] 2AI(Xf) + 30(Xf) = AlzO3(s ) (Eq 24)
O T 1695 OC [53Gok]
o -1.5 9 T 1723 ~ [65McL]
with
,7 T = 1600~ [70Fru2]

1
-2.0 K= (Eq 25)
(X Alf:,l)
2 (X 3 f 3 )
et0
-2.5 and
o
1 2 2 3All
-3.0
/

-3.5
-3.0 -21.5 -21.0 ' -11.5
log(Aluminum, Weight Percent)
Fig. 6 Alumina solubility in liquid iron at various temperatures
considering the presence of three solutes, A1, O, and AIO.
and experimental aluminum partial molar enthalpies of mixing
are shown in Fig. 4. The agreement is good in both figures.
3.3 Fe-AI-O S y s t e m
The curves shown in Fig. 5 illustrate the calculated solubilities
of alumina in liquid iron at various temperatures obtained with
the Fe-A1-O model. The agreement between the calculations
and experimental data is good up to an aluminum concentra-
tion of approximately 0.3 wt.%. Aluminum-killed steel usually
contains less than this concentration, and the optimized pa-
rameters of this model are thus useful when performing calcu-
lations at low aluminum contents.
At a given temperature, the solubility of alumina exhibits a
minimum in the oxygen content. Similar minima have been
experimentally observed with other strong deoxidizers such as
chromium, titanium, and vanadium [69Fru, 70Frul, 70Fru2].
The shapes of the solubility curves have been attributed to the
activity coefficient expressions of oxygen in the liquid solu-
+ EA1,o(XAI -- XA1XO) + ~AI,A1,O(~I -- X2AIXo) (Eq 26)
-It.0 -0.5 0t0 0.5
When the solution is dilute, the activity coefficients in Eq 25
can be neglected, and an increase in the aluminum content, XA1,
produces a decrease in the oxygen content, X o. As aluminum is
added, the activity coefficients will however play an increas-
ingly important role since the values of the AI-O interaction
parameters are large. For example, the first-order interaction
parameter, eA1.O,calculated at 1600 ~ from the expression in
Table 1 yields -464. As a matter of comparison, eAI.A~equals
4.66 at this temperature. The activity coefficient of oxygen is
thus substantially decreased by aluminum additions denoting a
very strong attraction of the oxygen for the liquid solution. The
net effect is an increase in the oxygen content of the solution.
The maxima in the oxygen solubility shown in Fig. 5 are
caused primarily by the presence of a large positive second-or-
der interaction parameter, EO,AI,A1. From Table 1, the value of
this parameter at 1600 ~ is 10 128. Being so large and posi-
tive, its effect is to increase the activity coefficient of oxygen as
XAI increases and the tendency for oxygen to leave the solution
reappears.
The large and negative first-order interaction parameter, eO.Al,
indicates that short-range interactions between aluminum and
oxygen are strong, which could be interpreted as a tendency to
form clusters. The hypothesis that this phenomenon can occur
in liquid iron is not recent [42Mar, 43Zap, 47Che]. As illus-

20 Journal of Phase Equilibria Vol. 16 No. 1 1995

 Basic and Applied Research: Section I

Table 2 Solute M o l e Fractions in L i q u i d Iron in E q u i l i b r i u m w i t h P u r e A l u m i n a

Temperature, Gross mole fractions Actual mole fractious
t
oC X~t . 10s Xo - 105 XAI. 105 Xo ' 105 X~do - 105
1866 ...................... 18 57 15.6 54.6 2.4
18 54 15.7 51.7 2.3
48 28 44.8 24.8 3.2
54 27 50 6 23.6 3.4
118 20 113.0 15 0 5.0
1823 . . . . . . . . . . . . . . . . . . . . . . 15 37 13.3 35.3 1.7
20 30 18.1 28.1 1.9
47 24 43.7 20 7 3.3
68 19 64.3 15 3 3.7
138 15 132.9 9.9 5.1
1760 . . . . . . . . . . . . . . . . . . . . . 17 23 15.2 21.2 1.8
17 22 15.3 20.3 1.7
31 16 28 8 13.8 2.2
39 13 36.8 10.8 2.2
48 13 45.3 10 3 2.7
1723 ....................... 6 17 5.4 16.4 0.6
12 14 11 0 13.0 1.0
22 12 20.4 10.4 1.6
45 9 42.8 6.8 22
1695 ..................... 8 23 6.7 21.7 1.3
9 18 7.8 16.8 12
15 13 13 6 11.6 1.4
26 11 24 1 9.1 1.9
34 9 32.0 7.0 2.0
1600 ................................ 41 3 39.7 1.7 1.3
124 2 122.6 06 1.4
145 3 142 8 0.8 2.2
186 2 184 4 0.4 1.6
207 2 205 4 0.4 1.6
310 3 307.4 0.4 2.6
722 5 717 3 0.3 4.7
1743 11 1732.1 0.1 10.9
2855 17 2838. l 0. l 16.9

The gross mole fractionsat 1695, 1760, and 1866 ~ are from Gokcenand Chipman [58Gok]. Those at 1723 and 1823 ~ are from McLeanand Bell [65Mcl] Those at
1600 ~ are from Fmehan [70Fru2]. Acutalmole fractionsare optimizedvalues.

trated by Fig. 6, when A10 clusters were introduced in the
model, a good agreement between experimental and calcu-
lated values was obtained. This model does not possess large
interaction parameters so the minima in the solubility curves
cannot be explained from them. The presence of these minima
can h o w e v e r be interpreted as being the result o f a competition
between two reactions:
2AI(Xd') + 3 0 ( X f ) = A1203(s )
1 gen and aluminum contents. In fact the cluster mole fractions,
K=
and
AI(Xf) + O(Xf) = A I O ( X f )
XA,OfA,O
K-
(XA,fA,)(Xofo)
In a dilute solution, Eq 27 predominates, and an aluminum ad-
dition yields the decrease in oxygen content of the liquid illus-
trated by 1he solubility curve. Equation 29, however, becomes
increasingly important as the aluminum content rises. This is
demonstrated by the data o f Table 2, which are listed according
to increasing aluminum actual mole fractions, XA1, and de-
creasing temperatures. At a given temperature, an increase in
the actual aluminum mole fraction, XA1, leads to a steady in-
crease in XAIo while X o steadily diminishes. If the total oxygen
content (Xo + XAIO) is plotted as a function o f the total alumi-
num content (XAj + XAjO), curves of the shapes depicted in Fig.
6 are obtained. Comparison of the values o f the actual mole
(Eq 27) fractions of the three species shows that there are relatively
few clusters in the solution at the experimentally reported oxy-
(Eq 28)
XAIo, outnumber the oxygen mole fractions, X o, only in the
data at 1600 ~ obtained at relatively high aluminum contents.
The fact that there are few clusters at low aluminum contents
(Eq 29) explains why the Fe-AI-O model yields satisfactory results up
to about 0.3 wt.% (X~I ~ 0.007). Also, there is a tendency for
the clusters to dissociate as the temperature increases. The be-
(Eq 30)
haviors described herein are consistent with the Le Chatelier
principle applied to Eq 27 and 29.
There are no m a x i m a in the oxygen contents yielded by the
equations of the cluster model of optimization No. 2. This con-
trasts with the results of optimization No. 1 (see Fig. 5) and the
calculations of H o l c o m b and St. Pierre [92Hol], who also util-

Journal of Phase Equilibria Vol. 16 No. 1 1995 21

S e c t i o n I: B a s i c a n d A p p l i e d R e s e a r c h

32.0 i i i i i
-1.0 , I , i ' i i i i
o T = 1866 ~ [53Gok]
9 T = 1823 ~ [65McL] -- Optimtzauon #3 31,0 J A N A F [85Cha]
~x T = 1 7 6 0 ~ [53Gok] ..... Opttmtzatton #1 ~
~o O T 1695 ~ [53Gok] 30.0 ..... Optimizatton #2 ~fL,"
o-- -1.5 9 T = 1723 ~ [65MeL] / /, ..... Optimlzatton #3 ~ ' ~ ~~
v T = 1600 ~ [70Fru2] / / /
29.0

g 28.0
~ 2.0
O 27.0
,-1
26.0
; ~ -2.5 '
25.0

o 24.0
~ -3.0
23.0

22.0 I I , 510 I J I.
-35-3.0 -2'.s -2'.0 -I',5 ' -1'.0 ' -0'.5 0'.0 0.5
5 46 48
10000/T (K)
52 54 55

log(Aluminum, Weight Percent)

Fig. 7 Alumina solubility in liquid iron at various temperatures Fig. 8 Logarithm of the equilibrium constant as a function of the
considering the presence of four solutes, AI, O, AIO, and Al20. inverse temperature for the reaction 2AI(I) + 3/202(g) = A1203 (s).

Table 3 Solute Mole Fractions in Liquid Iron in Equilibrium with Pure Alumina at 1600 ~
Gross molefractions Actual mole fractions
X~d 9 10 5 X~) 9 |0 s XAI - 105 X O - 105 XAI O " 105 XAI20 ' 10 s

41 .................................. 3 39.65 1 67 1.31 0.02

124....................... 2 12251 057 1 37 0.06
145............................. 3 142.63 0.75 2.13 0.12
186............................... 2 184 29 0.40 1 49 0A1
207.............................. 2 205.25 0.37 1.51 0.12
310 ............................... 3 307.10 0.38 2 34 0 28
722.............................. 5 716.19 0 25 3.69 1 06
1743............................... 11 1727 63 0.17 6.29 4.54
2855 ............................... 17 2828 77 0.12 7 53 9.35

The grossmole fractionsare from Fmehan[70Fru2].Actualmolefractionsare opumizedvalues.

ized a cluster model, In their work, the oxygen activity coeffi-
cient was described with an exponential function while that of
aluminum was kept constant throughout the whole composi-
tional range. Note that in this work the maxima appearing in
Fig. 5 are mathematical consequences of the model that con-
tains no clusters. At this time, there are unfortunately no reli-
able experimental data to validate the presence of maxima in
the oxygen solubility. D ' E n t r e m o n t et al. [63Den] reported a
decrease in the oxygen solubility when the aluminum concen-
tration approached 10 wt.% but attributed this phenomena to a
loss of a l u m i n u m and oxygen by distillation from the melt. The
results of these authors at lower aluminum contents were not
considered in this work because their scatter was too large, and
they moreover strongly disagreed with the other studies. Addi-
tional experimental measurements would therefore be re-
quired to elucidate whether maxima in the solubilities exist or
not. However, experimental studies by Hilty et al. [55Hil] and
Fruehan [69Fru] on the Fe-O-Cr liquid system in equilibrium
with an oxide phase reported no maxima in the oxygen con-
tents even when the chromium content reached 50 wt.%. Fe-O-
A1 solutions probably behave in the same manner.
The composition of the AIO clusters chosen in the model de-
scribing optimization No. 2 was based on the assumption that
in a fairly dilute solution the formation of small clusters should
be favored over large ones. An AIO cluster can be pictured as
an aluminum atom with one oxygen atom as nearest neighbor;
the other nearest neighbors are iron atoms. An interaction pa-
rameter between A10 and A1, eAIO,Alin Table 1, was required to
reproduce the experimental results at the higher aluminum
contents. The presence of this parameter was interpreted to re-
flect the attraction between A10 clusters and AI atoms. This
could lead to a tendency to form A120 clusters as the concen-
tration in aluminum increases while that of oxygen remains
relatively low. The Fe-A1-O-AIO-AI20 model was formulated
to test this hypothesis. Table 3 lists the optimized actual mole
fractions of the species at 1873 K for this model. Observe that
when the aluminum concentration is low there are few clusters
in solution. As the aluminum content increases, so does the
concentration of clusters, the n u m b e r of AIO clusters being at
first greater than that of AI20. However as the aluminum con-
tent rises, the mole fractions of A h O clusters become greater
than those of A10. The calculated alumina solubility curves
obtained with this model are shown in Fig. 7. As in the case of
the Fe-AI-O-AIO model, the Fe-A1-O-AIO-AI,O modcl also
reproduced the experimental results satisfactorily. The latter
model could, however, provide a better picture of the configu-
ration of the atoms in the liquid. In this model, the liquid phase

22 Journal of Phase Equilibria Vol. 16 No. 1 1995


is virtually ideal; i.e., the excess Gibbs energy of the solution is
small, the only interaction parameters in this model being eALAl
and eALALAI'Additional experimental data with iron alloys rich
in aluminum would be useful to confirm the clustering tenden-
cies discussed above. The results of Table 3, however, indicate
that clusters of different compositions appear to coexist in the
melt, and their concentrations at a given temperature and pres-
sure depend on the value of their respective equilibrium con-
stant.
The optimized data with the three models should yield expres-
sions of standard Gibbs energies of formation of alumina that
are consistent with those calculated in the pure substance tabu-
lations of J A N A F [85Cha]. The curves in this figure were cal-
culated by considering the summation of the following three
reactions:
2AI(X#") + 30(Xd3 = A1203(s)
2AI(I) = 2A__!I(Xd)
~ 9 2 ( g ) : 30(Xf)
to yield:
2Al(1) + ~)2(g) : A1203(s) (Eq 3 1
The standard Gibbs energies of the first reaction in Eq 31 were
calculated using the reported alumina solubility data at various
temperatures [53Gok, 65Mcl, 70Fru2] along with the interac-
tion parameters of the models given in Table 1. The standard
Gibbs energies of the next two reactions were calculated with
the Henrian activity coefficients in Table 1. A least square fit
was then performed to yield the three curves describing Eq 32.
4. Conclusion
Thermochemical parameters describing the iron-rich liquid
corner of the Fe-O-A1 system were optimized. The properties
of the system were well described by assuming that clusters are
present. The optimized data can satisfactorily reproduce the
solubility of alumina in liquid iron. The results obtained in this
study indicate that clusters of different compositions appear to
coexist.
Acknowledgments
This paper is based upon a thesis by D. Bouchard in partial ful-
fillment of the requirements of the degree of Philosphiae Doc-
tor at Ecole Polytechnique. D. Bouchard is grateful to
Professor A.D. Pelton of the Drpartement de Mrtallurgie et de
Grnie des Matdriaux, Ecote Polytechnique, Universit6 de
Montrral, for useful suggestions. Partial financial assistance
from the Natural Science and Engineering Council of Canada
is acknowledged.
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23