ISIJ International, Vol. 34 (1 994), No. 2, pp.

177-185

Assessmentof Aluminum-OxygenFquilibrium in Liquid lron and

Activities In CaO-Al203-Si02 Slags

Sung-WookCHO
and Hideaki SUITO
Institute for AdvancedMaterials Processing. Tohoku University. Katahira. Aoba-ku. Sendai. Miyagi-ken, 980 Japan.
(Received on September9. l993, accepted in final form on October 2~ l993)

The equilibrium constant KAI for the reaction: 2~l + 3~=AI203(s) and the first-order interaction parameter
e~1
were estimated at 1873 Kby using the values for the contents of oxygen, aluminumand other components
obtained in slag-metal equilibrium experiments and those for activity of alumina, along with the respective
interaction parameters. The values for log KAI and e~l were found to be 13.3~0.59 and -6.83~0.07.
respectively.
Activities of slag components in the CaO-Al.03-Si02 system were also evaluated at 1873 Kfrom the
values for nitride and sulfide capacities coupled with nitrogen and sulfur distribution ratios. These results
were discussed by comparing with previous values.
KEYWORDS:
slag-metal equilibrium; activityj deoxidation; distribution ratio; Ca0~].03-Si02 slag;
nitrogen, Sulfur

1. Introduction 2Al+3Q=Al203(s) ........ ..........

(1)

of great importance in order

Slag refining in the ladle is
Fromthe equilibrium constant Kl of Eq. (1), the apparent
to produce high-quality, clean steels. Knowledge of
thermodynamic properties, such as the activities in
equilibrium constant, Ki
{
= [masso/o Al]2 [masso/o
O]3},
and the first-order interaction parameters, the following
.

CaO-Al203-Si02 slags whose values by Rein and relation is derived,

Chipmanl) are commonlyused, is required for the better
understanding of the deoxidation and reoxidation
10g Ki + 2~eAXl[masso/oX] + 3~e~[masso/oY] - Iog aAl,0=
phenomena. Although there have been a number of =
-eAOl{2[masso/o O] 1.78[masso/oAl]} -10g Kl "(2)
+
available data on activities, deoxidation equilibrium
constants and interaction parameters in relation to ladle
where Xand Y
represent componentsother than and O
A1, respectively.
refining, these values are still not unambiguously de-
termined due to experimental difficulties.
Thevalues of e~6,8,9) used in this study are summarized
in Table 1. In the derivation of Eq. (2), the terms with
This paper deals with the assessment of the activity
respect to the second-order interaction parameters, the
values in CaO-Si02, CaO-Al203and CaO-Al203-Si02
slags, the equilibrium constant KAI for the reaction: oxygen self interaction parameter, the effect of calcium
2Al + 3Q=Al203(s) and the first-order interaction on oxygen and aluminum and that of magnesiumon
parameter e~1' based on the results obtained in oxygen are neglected. A
Iinear relationship with a slope

previous2 ~ 7) and present sla~~metal equilibrium experi-

1
ments at 873K. In the estimation of activity,
following three procedures were used; 1) the relation
betweennitride capacity, C(N)
{=
(masso/o N) P~/4/P~/2},
of -eAol and an intercept of -log Ki is expected in a
plot of the left hand side of Eq. (2) vs. {2[masso/o O] +
the
1.78[masso/o Al]} term, if the assumption madein the
derivation of Eq. (2) is valid. The relation between
•

~)/ the left hand side of Eq. (2) and {2[masso/o O] +

and nitrogen distribution ratio, LN = (masso/o
[masso/o N]}, 2) the intercept of the line in a plot of
{ l.78[masso/o Al]} term is plotted in Fig. 1, using the

the relation between the activities contents of oxygen, aluminumand the other components
of metal components
obtained in previous equilibrium experiments3~7) and
in liquid iron and 3) the relation between sulfide capaci-
the present experiment whoseresults are given in Table
ty, Cs'-{=(masso/o S) P~/2/Psl/2}, • and sulfur distribu-
~)/[~asso/o 2. Experimental details are described elsewhere.4'7) For
tion ratio, Ls
{=
(masso/o S]}.
the values of aAl,0= given in Table 3, the Rein and
Chipman's valuesl) were used except for those in
2. Equilibrium Constant of AluminumDeoxidation and
Interaction Parameter CaO-MgO-Al203slags.7) The slag compositions in
CaO-Al203-Si02 and CaO-Mg(l~Al203 systems are
Deoxidation equilibrium for aluminumis given by denoted by AC, CA, ACS, CAS(see Fig. 9) and ACM,

177 C 1994 iSIJ

 ISIJ International, Vol. 34 (1 994), No. 2
MAC.CAM(see Table 2), respectively. The ranges I, CAM).This indicates that the effect ofcalcium on oxygen
II, and 111 shownin be explained next.
Fig. I will is
so strong in the slags with high calcium content, since
The data points in the range I represented by a the terms with respect to the second-order and the self
half-filled mark were neglected in drawing the line. The interaction parameters are negligibly small.
reason for this will be described later. As can be seen The calcium-oxygen equilibrium in liquid iron was
from Fig. 1, the positive deviation from the line was ob- studied by Kimura and Suit06) using a slag-metal
served for the data in CaO-saturated slags (CA. CAS8, equilibration technique. They estimated the values for
the equilibrium constant Kc* for the reaction: CaO(s)
=
Table 1. Interaction
present work.
parameters at 1873K9) used in the
Q
~~+ and the first-order interaction parameter eg• (eco.)
by using the values for the intercepts and the slopes
obtained in three different ranges I, 11 and 111. These
j results are shownin Fig. in which the present data are 2
Al S 0.030
Si 0.056 o~
,N
Al 0.045 ~
co
_6

O Al -3.9 eJO Acs2

Si -0.131 ~ Acs4
[S]

S -0.133 I -8
Q CAs5
Ca (Table 4) ~ X cAs8
N
~~s)
+ cAs9
Al
- 0.028
-o
~o
_10
X
Si
Si

S
O.047
0.056
F~l
cr) _12
AVAA
~{~~~;]~/A~,1itJ~1
.40~r~[]
o v
Al 0.058
+ .,
Si O.
11 -~~>.:~~]
_
>
~: RangeI u,
m
-14
Ca S 140*
--0.072
~ ~!~~.~~
Ac o o
Al >
CA A ~
Si -0.097 ACM[] r]
~16
O (Table 4) ~l
c~]
MAC ~>

S S -0.028 + CAMv v
Al 0.035 ~~ -18
Ca -I lO* eJO
o
O O.1 O.2 0.3 0.4 0.5 0.6
Si 0.063
2[%O]+1.78[%Al]
* Ref. 8) Fig. l.
A plot for the relation expressed by Eq. (2) at 1873 K.
Table 2. Chemical compositions of metal and slag phases obtained in the present experiment,

Metal Slag
[Si] [Mg] [Al] [Ca] [O] [N] (N) (Ca) (Si) (Al) (Mg)
(o/o) (p pm) (ppm) (o/')

ACS2
O,
177 30.3 0.41 39.6 171 17.1 16.4 11.7 27.5
0.183 42.8 0.62 38.0 145 21.8 16.3 lI.4 28.0
O, 140 12.3 0.41 59.4 l 27 13.7 16.2 ll.6 28.1
ACS4
0,800 46.0 1.36 13.7 l 28 57.8 21.4 7.0 29 . 1
O. 93
1 20.5 1.17 25.3 427 69 . 6 21.7 7.4 28.7
0,198 17.7 l.33 23.3 396 76.0 22. l 7.2 28.2
CAS5
O,0571 80.0 2.54 3.1 l 69 52.0 38.2 7.8 15.9
0,176 78.6 3.22 3.9 155 156 38.5 8.0 15.8
O, 12
1 56.4 2.40 4.7 252 lll 39.0 7.3 15.6
CAS8
0,743 1750 15.6 l .8 63.6 143 45.1 3.9 14.8
O.
132 89.8 8.82 2.5 119 69.4 44.3 4.
1 15.0
ACM
0.44 1110 1.52 3.1 49.4 136 21.1 36.0 2,
l
0.32 339 3.38 4.6 177 163 20 . 8 36.5 2.3

MAC 0.20 20.2 1.49 8.2 90 . 2 9.5 22.9 29. l 7,8

0.21 9.33 l .34 9.1 68.6 l I .4 23.l 29.0 7.6

ACM
: 30 Imass .
o/o
Ca0-66 3masso/o A12O3-3 2masso/o MgO
. '

MAC:31.7masso/oCa0-52.9masso/oAl203-14.8masso/oMgO
CAM
: 54 8mass .
o/o Ca0-385masso/o Al 2O3-6 8masso/o MgO
. .

C 1994 ISIJ 178

 ISIJ International, Vol. 34 (1 994). No. 2
not included and the values for Kc* and eg•6) are
summarizedin Table 4.
containing MgO. The value for eAOI
= _ 6.83~0.07)
obtained from the slope of the line shownin Fig. I agrees
(
Whenthe effect of calcium on oxygen was taken into well with the reported value of eAOI (= 6.69)). The
account to obtain the data points in the range I in Fig.
_
standard deviation of eAOI
was obtained as 0.07 in the ~
l by using Eq. (2), the data points were found to scatter range of {2[masso/o O] + 1.78[masso/o Al]}>0.1. The
considerably. This is thought to be due to the extremely equilibrium constant for the Reaction (1) in logarithmic
high value for eg•
(
= - 5OOO).Therefore, the data points
in the range I were neglected to estimate the values for
form was estimated as 13.3+0.59 at 1873K from the
intercept of the line, which is in excellent agreementwith
eAOI
and K1 It should be noted that in the equilibrium
'
the reported value of logK1 (= 13.39'10)).
(
given by Eq. 1) the interaction parameters given in Ta-
ble 4 cannot be used for the data in the ranges 11 and 3. Activities in CaO-Al203-Si02 Slags
III. This is because these interaction parameters are
linked up with the values for log Kc* which have no
3.1. Estimation from Nitride Capacity and Nitrogen
Distribution Ratio
thermodynamic meaning. Furthermore, the effect of
magnesiumon oxygen should be considered in the slags A gasslag reaction for nitrogen can be written in an
ionic form for free nitride,
Table 3. vatues for a^*,., *) c(N)**) and c~,-'6) at 1873K. 1/2N2 + 3/2(02-) = (N3 ~) + 31402 """""""(3)
Slag aAl203 log C(N) 10g Cs2- and for incorporated nitrogen
ACS2 0.81
- 11.09 l/2N2+2(O~)=(N~)+ l/2(02~)+31402 """'(4)
ACS4 0.60
- 11.64
CAS5 0.063 12.05 Without respect to the form of nitrogen in slag, however,
-
CAS8 0.0048
- 12.94 nitride capacity C(N) rs defined as,
CAS9 O.066
- II ,84 P~/4/ P~/2
CS - I 1.50 (- 3.45) C(N)
~ (masso/o N) '
, . . . . . . . . .
(5)
AC 0.33
- 12.20 3.48
- The ~i/Si02(s) equilibrium can be expressed by
CA 0.0048
- 12.91
-
2. 05
ACM 0.51*
MAC O.09*
CAM 0.0003* AG~=-816200+216OT (J/mol)9 Io)

* Ref. 7), and the nitrogen dissolution reaction in liquid iron is

() See text. written by

tt
o~
I
~
II III
-4
bJ) l l
o
l
-5 l
l +~~~l~~7F~E~i+O'~o o
~i~~s0>~o tlOOD-lO-~~~
,t:~
~~:~)
-6
l
- l
~i~~;( []
o(J 'A[]D~ ~> Acs2
P~I -7 ~l ACs4
+
~)~;'*~*+~
~~~:1~~
o Q CAs5
~~~c) -8 X CAs8
~ + cAs9
~(Do
vv o cs
~9
-9 O Ac
+ [% Al] O.3 ACA
~,~ -10
[] ACM Fig. 2.
[9if~'
Si] 1.0
~ MAC
eJ)
o v CAM A plot for the deoxidation equilibrium for calcium at
-11 tt 1873 K.6)
o o002 o004 o006 o008 o,cn o.015 0.020

[%Ca] +2.5 1[%O]

Table 4. Values for Kc* and eg• at 1873 K.6)

Range* [olo Ca] +2.51 [~/o O] log Kc* ca
eo o
eca log K12* *

I o.o008
-7.6
10.3
- 5ooo + 400 - 13OOO l 6.0
- 1500
II o.o008 o,003
- - + 0.3 - 600+ 80 l0.6
III
> o.003 -
5.8 + 0.3 -60+4 - 150
7.0

* See Fig. 2.

** FromKc" K6 and K09) (for ll202=Q)'

179 C 1994 ISIJ

 ISIJ international. Vol. 34 (1994), No. 2
from a gas-slag equilibration technique,ll) nitrogen
l/2N2=~ ••••••••••••,••••••••••••••••••••••••••••••••••••••..•(7)
distribution ratio, the Si and Al contents obtained from
AG~= 3600+23.9T (J/g'atom)9) the supersaturation experiments4) as well as present
By substituting Po, and PN, obtained from Eqs. (6) and (Table 2) and previous equilibrium experiments4) and the
(7), respectively, into Eq. (5), the following relation is respective interaction parameters listed in Table I .

derived fN4/3 asi/K~/3)

log asio,
= 4/3 Iog(C(N)/LN) + Iog(K6 ' .

C(N)=LN'(K7 as3,/04,)/(K3/4 fN a~,/4) ..........(8)

.
(9)

where LN is the nitrogen distribution ratio defined as The values for log C(N) used in this study are listed in
(masso/o N)/[masso/o N] and the values for K6 and K7 are Table 3. The log asio, values were calculated from Eq. (9)
the equilibrium constants for Eqs. (6) and (7), re- as a function of log[masso/o Si]. The results are shown
spectively. The values for ai and fi are the activity and in Fig. 3, in which the values of Rein and Chipmanl) are
the activity coefficient of i component, respectively, in also indicated by an arrow mark. The asio, values for CS
liquid iron with*respect to a dilute one masso/o standard slags will be explained in Chap. 4. As is clear from Fig.
state .
3, the asio, values agree fairly Rein well with those of
The values
for asio, relative to the solid standard state and Chipman.
can be calculated from the following relation given by The values for aAl,0= and ac*o can also be calculated
Eq. (9), using the values for nitride capacity obtained in a similar mannermentioned above by using the values
for C(N) and LN, the A1 and Cacontents and the respective

1)o CS ACS2 1873K

interaction parameters listed in Tables I and 4. The
> CAS8 ACS4
E~l

+ CAS9 Q CAS5 O
~1)-O-oTF(:~~>0 *HF Rein & Chipman
O ~!' t~l
~l
~]_r~[E~~l-
-2
L~~]~l
1873K 2
O -2
o
o + o
O_

CO
X X -4 ~i-=
-2
X O
eJ)
O
o -6
~ *'---'~~f
-4
l~~;~~~~)~
~~
eJO
O X X
~]E~E!ir~],_.
2
~7[E~~1[E~l
-2 -~I
~~I r~]
o ~~~,-~-/??~'~~\~~_
~>~ ~ Acs2
_Q,Q_~!_S!_~)j~ Q Q
E;1
Acs4
Q G))~ Q
-4 -2 ~tQ~QQ(~)-Q- X
cAs5
cAs8
-~ Rein &Chipman Q C~)
+ cAs9
-3 -2 -1
O 1 -4
-4 -3 -2 -1 O
log [%Si]
log [%Al]
Fig. 3. Activity of Si02(s) calculated from Eq. (9) vs. silicon
content in logarithmic form. Half-filled marks re- Fig. 4. Activityof Al203(s) calculated by using the values for
present the data calculated by using the values for Cs' - C(N)11)and LN vs, aluminium content obtained from
and Ls'2) present and previous4) works.

Table 5. Estimated activities relative to the solid standard state in CaO-Si02, CaO-Al203 and CaC~Si02~1203slags at
1873 K.
from C(N) and LN (from Cs2- and Ls) from intercepts in Figs. 5and 6
Slag
log asi02 log aAl203 log acao log aA~203 log acao

ACS2 + 16 - I ,43 + O. 13 + O. 11 +0.14

+ O. 10 1.69
- O.63 0.63
.68
- 0.97
O. O,
- -
ACS4 - I .99 + 0.23 O.95 + 0.40
- .87 +0.41 - I + 13 - 0.99 + O. Il - l.44 +0. 14
CAS5 -3.39+0.15 I -0,1 1+0,33 I,92 +0, 12 -0.067 + 0.35
- 3.35 -
CAS8 -4.5 1+ 0.22 -0.93 + 0.83 -3.18+0,17 0.82 + 0.76
- 0.62 + 0.66 -
CAS9 - 2.34 + 0.07 - + O. 13 - I .60 + 0.40
,OO 0,49
- 0.76 + 0,30 -
1.37 +0.02
CS - I .20 + O. 17* I
- .08 + O.
AC - 0.57 + 0.23 - I + 13
(- 0.90 ~0.23)
CA - 2.82 + 0.4 1
- 15+
O. O.44

(- 2.62 ~0.40)
* Values obtained from Cs' - and Ls are included.

C 1994 ISIJ 180

 ISIJ International, Vol. 34 (1994), No. 2
results for aAl,o, are shown in Fig. as a function of 4 Activities of A1203in CaO-A1203-Si02Slags relative
log[masso/o Al]. It can be seen that the results obtained to the solid standard state can be calculated from the
are significantly different from those reported by Rein intercepts in Fig. 5, by using the equilibrium constant
and Chipman,1) despite the fact that those for asio, are Klo and the asio, values obtained from C(N) and LN. These
in satisfactory agreement with their values. This dis- values are summarized in Table 5. The aAl,o, values
crepancy is not certain at present. The values for asio,, obtained from intercepts are in good agreement with
aAl,o, and ac*o are summarizedin Table 5. those obtained in Sec. 3.1.
3.2. Estimation from the
Re]ation between Metal
The siliconcalcium equilibrium is expressed as,
Componentsin Liquid lron 2~~~+Si02(s)=2CaO(s) +~i •••••••••••••••(12)

The silicon-aluminum equilibrium can be expressed Using the equilibrium constant K12 of Eq. (12), the
by Eqs. (1) and (6) as,
following equation is derived.
3Si+ 2Al203(s)= 4~l + 3Si02(s) .................(10) log ac* + I/2 Iog K12
AGl0=65.8300-107.2T (J/mol)9'10)
= I/2 Iog aSi + I/2 (2 Iog ac.o ~ Iog as,o ) (1 3)
Using the equilibrium constant Klo of Eq.(lO), the fol-
lowing relation is deduced. In the equilibrium given by Eq. (12), the interaction
parameters given in Table 4can be used, if the equilibrium
log aAl
= 3/4 Iog asi constant K12 is modified by the respective values for Kc*'
+ l/4(2 Iog aAl,o, ~3
Iog asio, + Iog Klo) -"-'(1 l) The values for ecO. and log K12 given in Table 4were used
for the calculation of the left hand side of Eq, (1 3) using
The values for aAl and asi Werecalculated by using the
A1 and Si contents obtained in the present equilibrium the previous4) and present equilibrium results, along
experiments and the previous equilibrium and super- with the values for the A1 and Si contents below O.3 and
saturation experiments4) together with the respective 1.O masso/o, respectively. Thesevalues are plotted against
interaction those for log asi in Fig. 6, where a linear relationship with
parameters. The relations betweenaAl and asi
in logarithmic form for different slag compositions ar'~~"e a slope of l/2 as predicted from Eq. (1 3) is approximate-
ly observed except for CAS8slags. Activities of CaOin
shown in Fig. 5, indicating the linear relationship with
a slope of 3/4 as predicted from Eq. (1 l). It should be
CaO-A1203-Si02slags relative to the solid standard
pointed out that the values in equilibrium experiments state can be obtained from the intercepts in Fig. 6, by
using the equilibrium constant K12 and the asiO, values
agree well with those in supersaturation experiments
represented by a half-filled obtained from the values for C(N) and LN. These values
mark. This suggests that the
reaction expressed by Eq. (lO) is not affected by the are given in Table 5. The ac*o values obtained from the
intercepts agree closely with those obtained in Sec. 3.1.
content of oxygen.
The values for asio, are plotted in CaO-Si02-AIO1.5
-1 phase diagrarn in Fig. 7, indicating the reasonable
ACs2
agreement with those of Rein and Chipman.1) However,
the values for aAlo*:= and ac.o Plotted
L9 ~] Acs4 in Figs.
8 and 9,
_2 o~ cAS5
o
A~ CAs8
+ cAs9
~ Acs2 1873K
*3 -1 ~! Acs4 3
~) cAS5
X
'~~\'_

/A\ X cAS8
X 2
l)~1:/A/ + cAs9
~1 l! Ir> -2
1
cu /2~ ~E~i
~l!J1 x+
ll'~/ItA
X
~ l!~i]
'*F_r~l
/ c~
~~
X
O
-1
~
IL
/ e~~)/Q'~l~/
*3 eJ)
O
c~
3 -1

~Ll!
-2 -4
+ 2 ~)-Q;/_/11
Q ~l
~
nj]

oi)'~ ~1 ~~e)
('1 ~O Q 2
O
*3
~1 ~i~~)j>~>
O
E~1~1*~l~/Eg
~g~/
If~
~~

17r ~ 1873K
-1
lr:~~~ _/~~;~:~ep!~

-4 *2
*3 -2 - 1 O 1 v
-3
log aS!:
*2 -1 O 1
Fig. 5. Relation between aAl and asi logarithmic form
expressed by Eq. (1 l). Half-filied
m log asj
marks represent the
data for the supersaturation experiments.4) Fig. 6.
A plot for the relation expressed by Eq. (13).

181 C 1994 ISIJ

 ISIJ lnternational, Vol. 34 (1 994). No. 2
asi02 SiO 2

cs S2A6
(0,063
40
0.20
C3S O. 10
C2S .
05 Al O1.5
CAS9 0.025
80
ACS2
(O,0046) 0.010 (0.11) 20
'\_ACS4
CAS5 0.005 Fig. 7.
(0,00041) 10-3 (0.010) CAI2
CaO CAS8
(0,000031) .\ 10 -4 CA4
Activities of Si02(s) along with the values of Rein
and Chipmanin CaO-Si02-AIO1.5 phase diagram
at 1873 K.
CaO 20 40 60 80 AIO1.5
(mol %)

aAlol'5 SiO 2

S2A6
60 40
/ ,,/,
O. 25
C3s
C2S AIO1.5
CAS9 O.75 ACS2
80 (0.46) ,,
20
(O.48)

CAS5 ACS4 CAI2

(0.11) (0.33) Fig. 8.
CaO cAS8 Activities of AIO1.5(s) along with the values of Rein
(0.024) CA4
and Chipmanin CaO-Si02-AIOi Phase diagram
5
CA at 1873 K.
20 AC
CaO (0.042)
60 (0.44)
80 AIO1.5
(mol 9{:.)

a(~o SiO 2
0.003
S2A6
cs 0.005 40
(0,025~
0.01
C3S 0.02 \\
80
C2S
CAS9
(0.072)
0.05 \\ \ ACS2
\(0.021)
Al O1.5

20
CAS5 O.
I
0.82 ACS4 CA12 Fig. 9.
(O.037) Activities
0.2 of CaO(s) along with the values of Rein
CaO CAS8 0.5
CA4
(0.13) O and Chipmanin Ca(:~Si02~101.s Phase diagram
at 1873K.
CA AC
CaO 20 (0.71)
60 (0.083)
80 AIO1.5
(mol %)

which are the average values obtained in above Figs. IO 1

to 2. The experimental uncertainty obtained in
mentioned two methods, are significantly different from the values of ac,o, aAl,o, and asio, Ieads to the marked
those of Rein and Chipman.1) deviation from the previous values of AG;-
The free energy of formation (AG;) of CaO6Al203, '
The activities of Si02 in logarithmic form at the slag
CaO2Al203 and 2CaOSi02 are shownin Figs. 10, 11
' ' compositions saturated with lime and alumina crucibles
and 12, respectively. The free energy of formation of are plotted against the mole fraction of Si02 in Fig. 13,
CaO6Al203 Wascalculated by using the present values
'
along with the results by other investigators.1'20,23,24)
for ac.o and aAl'o, obtained in ACS2slags. The AGf The values by other investigators except for those of
values for CaO2Al203 (ACS4, AC) and for 2CaOSi02
' '
Rein and Chipman1) were recalculated using the same
(CAS5, CAS9)were also calculated by using the present value of AG~as that of Rein and Chipman.1) As can
values for the respective activities. As a result, the values be seen from Fig. 13, the asiO, values estimated in the
of 197.5 kJ/mol for ACS2(CaO 6Al203), 120. I kJ/ present study agree well with those of Rein and Chip-
-
mol for ACS4(CaO 2Al203),
-
90.5kJ/mol for AC
'

- '
manl) and Kay and Taylor.24) The reason for the dis-
(CaO 2Al203), 127.7kJ/mol for CAS5(2CaO Si02) agreement of the present estimated values for aAl,o, and
'

-
and 165.8 kJ/mol for CAS9(2CaO Si02) are markedly
'

- '
ac*o With those by Rein and Chipmanis not clear at
different from those of previous worksl'l2 ~ 22) shownin
present, although the relation between the activities of

C 1994 ISIJ 182

 ISIJ International, Vol. 34 (1994), No. 2
o o
CaOeruc. Al203 cruc.
-1
v.~('~/

A~I
//
Allibcrt ct al.

~!
o
~
-50
~~\
Hailstedt Nagata et ai. Fujisawa
O
ct al. 6~~
-2

/
/
/
~
Kumar& Kay COc'o
/ /
.~ _3
/
,* eJ)
O O
-100
-4
/

CaO•6A 12O3 -5
~ 1873K
/
Rein& Chipman -- -- •
Langenbergct
Ozturk
al.

& Fruchan
-150 Kay &Taylor O This work
80O 1200 1600 2000 -6
O 0,2 0.4 O O.2 0.4
Temp./ K
XSi02
Fig. lO. The free energy of formation of Ca0•6Al203 from
solid CaOand Al203.12- 15,18] Fig. 13. Logarithm of activity of Si02(s) vs, mole fraction of
Si02 at 1873 K.

o 2
1873K c:~o
o
Allibcrt Fujisawa ct al.
O
~ti
et
r OO
(~c~~d!~)~r:;_*~i~l~~D~)(?,(?~O~

~\_ ~-Kumar&Kay camcronet al. AC

'!~)

-
'
~~5'~C~'i~)

~-~
1)O'-•,t~~ 'f~L~~_.J"'O.:iJ_

l'\. Nagata ct al,

j-C] O (D) *1
o~ -50 H~tllstedt
Ot
'D ti)
--
1)O -2
:!~
o
Kor &Richardson o
O -3
*~
.*
~
Rcin & Chipman
~
eJ)
A
J:~

A J~JI~:~
-100 -2 ~
O J~..~
IL AA ~L_Is~c~~~;~L~A~efd:i~~~~,~~L_

-3 CA ~r~J~~: Al)~'A"~2~~~Ae~'~
~A
-4
~ ~
CaO•2Al 2O3 ~
-5
-15O
1200 1600 2000 -6
-~ Rein & Chipman
800
-5 -4 -3 -2 -1
O 1
Temp. /K log [%Al]
Fig. Il. The free energy of formation of Ca0•2Al203 from Fig. 14. Activity of Al203(s) vs, aluminum content in
solid CaOand Al203.1'12- 18)
logarithmic form. Open and half-filled marks re-
present the data calculated by using the values for

-50
C(N)11) and
L 3 6) and those for -26) and Ls'3,5,25)
C
respectively; Ieft half-filled marks by Inoue et a!.3)
and Tanabe and Suit05] and right half-filled marks
2CaO•SiO 2 by Ozturk and Turkdogan.25)

metal componentsshowsa good linearity and the values

os
-100 for aAl203 and ac.o obtained from the intercepts of the
lines are consistent with those obtained from the values
Langcnberg ct al.
~~ of C(N) and LN. Moredetailed study is necessary to clarify
.~ Barin et al. & Macfarlanc
Cartcr this discrepancy.
,*
~ -150 Rcin & Chipma~~~~l
Sharrna &Richardson 4. Activities in CaO-Si02and CaO-Al203Slags
4. 1. Estimation from Nitride Capacity and Nitrogen
Distribution Ratio

-200
The values for asi02 and acao in CaO-Si02 slags
800 1200 1600 2000 saturated with CaOcrucible (CS) and those for aAl203
and ac.o in CaO-Al203slags saturated with Al203(AC)
Temp./ K and CaO(CA)crucibles can be obtained from the results
for C(N)11) and LN2,3,6) in the
Fig. 12. The free energy of formation of 2CaO'Si02 from manner similar to that
solid CaOand Si02'1'19-22) mentioned in Sec. 3.1. The data in equilibrium experi-

183 C 1994 ISIJ

 ISIJ International, Vol. 34 (1 994), No. 2
ments where the Al and Si contents are below 0.3 and and Cs'- and Ls are -0.72~0.28 and -2.74~0.41 for
1.Omasso/o, respectively, were used to estimate the ac*o ACand CAslags, respectively, and these are in reasona-
values in CS, andAC CA
slags. The results are sum- ble agreement with the values of Rein and Chipman.1)
marized in Table The asiO, values in CSslags and the
5. The asio, values in CSslags can also be estimated in a
aAl,0= values in and AC CA
slags are plotted in Figs. similar mannerusing the values for Cs'- and Ls' Since
3 and 14 by an open mark, respectively, indicating a the Cs'- value for CSslags is not available at 1873 K,
reasonable agreement with the values by Rein and this value
was estimated to be - 3.45 from the results
Chi pman.i ) obtained at 1773K by Carter and Macfarlane21) and
4.2. Estimation from Sulfide Capacity and Sulfur Dis- Sharmaand Richardson22) and those obtained at 1923 K
tribution Ratio by extrapolating the Cs'- values of Fincham and
Richardson27) and Abrahamand Richardson28) to the
Agas-slag reaction with respect to sulfur can be written
2CaOSi02 • saturated composition, whereas the values
in an ionic form as,
by Carter and Macfarlane21) and Fincham and
Richardson2 7) were corrected by the newersulfur-oxygen
ll2S2 + (02~) = (S2 ~) + 11202 """"""""(14)
gas equilibrium data.28) The Ls values by Inoue and
Using the equilibrium constant K14 of Reaction (14), Suit02)
sulfide capacity Cs'- is defined as, were used in this study. The results are shown
by a half-filled mark in Fig. 3, along with those from
Cs'- ~: (mass Vo S) P~/2/Pi/2 ...........(1 5) C(N) and LN by an open mark. Both results are in good
agreement with each other. It can be seen from Figs. 3
The ~!/A1203(s) equilibrium can be written by and 13 that the asio, value in CSslag agrees well with
Al+ 31402= l/2A1203(s) ...............................(16) those obtained by other investigators.1'20,24)
AG16=-776800+188.8T (J/mol)9'10) 5. Conclusions
and the reaction for sulfur dissolution in liquid iron is

represented by The following conclusions were derived from the

assessment of previous and present results obtained in
1/2S2 =~ ••••••••••••••••••••••••••••••••••••,,••,,•••,••••••••••(17)
sla~~metal experiments.
AG17= 135 100+23.4T (J/g'atom)9) (1) The equilibrium constant for the reaction: 2A1+
- 30=Al203(s) in logarithmic form and the first-order
By substituting Po, and Ps, obtained from Eqs. (16) and interaction parameter e~1 were estimated to be 13.3 0.59
(17) into Eq. (15), the following relation is derived ~
and -6.83 0.07 at 1873 K, respectively.
~activities
Cs'-
= Ls ' (K17 alA{~0,)1(K~~3 fs
' • '
a2A(3)
..........
(18) (2) The for Si02 in CaOAl203-Si02slags
obtained from the values of C(N) and LNagreed well with
where Ls is the sulfur distribution ratio defined as those reported by Rein and Chipmanand by Kay and
(masso/o S)/[masso/o S] and the values for K16 and Ki7 Taylor. However, the values for aAl,0= and ac.o Were
are the equilibrium constants for Eqs. (16) and (17), significantly different from their values.
respectively. The values for ai and fi are the activity and (3) The values for asio, in CaO-Si02slags and those
the activity coefficient i
of component, respectively, in for aAl=0, in CaO-Al203slags estimated from Cs'- and
liquid iron with respect to a dilute one masso/o standard Ls agreed with those obtained from C(N) and LN. These
state . values as well as the ac*o Values in CaO-Si02 and
The aA1,0, values in CaO-Al203slags can be estimat- CaO-A1203slags were in reasonable agreement with
ed from the following relation given by Eq. (19), using those by Rein and Chipman.
the Cs'- values obtained in slag-metal experiments2s)
or gas-slag equilibrium experiments26) at 867 K, and 1 REFERENCES
Ls Values obtained in slag-metal equilibrium experi- R. H. Rein and
l) J. chipman: Trans. Metatt, soc. AIME, 233
ments.3'5,25)
(1965), 415.
2) R. Inoue and H. Suito: Metall. Trans. B, 23B (1992), 613.
= 3Iog(Cs' a~l/KI
fs3
log aAl,o,
-
/Ls) +Iog(KI 6
' . 7)
3) R. Inoue, H. Inoue and H. Suito: ISIJ Int., 31 (1991), 1389.
.(19) 4) F. Tamuraand H. Suito: Metall. Trans. B, 24B (1993), 121.
5) J. Tanabeand H. Suito: CAMP-ISIJ, 6(1993), 1058.
In the present work, the Cs'- values by Hino et al.26) 6) T. Kimura and H. Suito: Metall. Trans. B, 25B (1994). Feb.
3
given in Table were chosen for and CAslags in AC 7) T. Kimura: Master of Engineering Thesis, Tohoku University,
order to estimate the aA~,0= values. The results are (1993).

5
summarized in Table and are plotted in Fig. 14 by 8) Recommended Values of Equilibrium Constant for Steelmaking
Reaction, The 19th Committee (Steelmaking), The Japan Soc.
a mark; a
half-filled mark by Inoue et
left half-filled
Promotion of Sci., Rep. No. 10588 (Nov. 1984).
al.3)and Tanabeand Suitos) and a right half-filled mark G. K. Sigworth and J. F.
by Ozturk and Turkdogan.25) The values of Rein and
9) EIliott: Met. Sci.,
8 (1974), 298.
l O) J. F. Elliott, M. Gleiser and V. Ramakrishna: Thermochemistry
Chipmanl) are also indicated by an arrow mark. It can 1
for Steelmaking, Vol. 2, Addison-Wesley, Massachusetts, 963)
( .

be seen from Fig. 14 that the results obtained from Cs'- 11) K. Tomiokaand H. Suito: ISIJ Inl., 31 (1991), 1316; Steel Res.,
63 (1992), 1.
and Ls agree with those obtained from C(N) and LN, al-
though the data points scatter considerably. The av- l 2) M. Allibert, C. Chatillon, K. T. Jacob and R. Lourtau: J. Am.
Ceram. Soc., 64 (1981), 307.
erage values of logaAl,o, obtained from C(N) and LN 13) R. V. Kumarand D. A. R. Kay: Metall. Trans. B, 16B (1985),

C 1994 ISIJ 184

 ISIJ International, Vol. 34 (1994), No. 2
l 07 .
York, (1958), 65.
14) K. Nagata, J. TanabeandK. S. Goto: Tetsu-to-Hagan~,75(1989), 21) P. T. Carterand T. G. Macfarlane: J. Iron Steel Inst., 185 (1957),
2023 .
62.
15) T. Fujisawa, C. Yamauchiand H. Sakao: Tetsu-to-Hagan~, 76 22) R. A. Sharmaand F. D. Richardson: J. Iron Steel Inst., 200
(1990), 368. (1962), 373.
16) J. Cameron.T. B. Gibbons and J. Taylor: J. Iron Steel Inst., 204 23) B. Ozturk and R. J. Fruehan: Meta!l. T,'ans. B, 18B (1987), 746.
(1966), 1223. 24) D. A. R. Kay and J. Taylor: Trans. Faraday Soc., 56 (1960), 1372.
17) G. J.W.Kor and F.D.Richardson: J. Iron Steellnst.,206 (1968), 25) B. Ozturk and E. T. Turkdogan: M:et. Sci., 18 (1984) 299.
700. 26) M. Hino, S Kitagawa and S. Ban-ya: Tetsu-to-Hagan~, 79 (1993),
18) B. Hallstedt: Am. Ce,'am. Soc., 73 (1990), 15.
J. 34.
19) I. Barin, O. Knacke and O. Kubaschewski: Thermochemical 27) F. D. Richardson and C. J. B. Fincham: J. Iron Stee[ Inst., 178
Properties of Inorganic Substances, Supplement. Springer-Verlag, (1954), 4.
Berlin and NewYork, (1977). 28) K. P. Abrahamand F. D. Richardson: J. Iron Steel Inst. 196
20) F. C.Langenberg. H.Kaplan and J. Chipman:Physicai Chemistry (1960), 313.
of Steelmaking, ed. by J, F, Elliott, John Wiley and Sons, New

185 C 1994 ISIJ